The invention relates to compounds of the formula: 
in which
(A) either
X is CH or N,
Y is OR1 and
Z is O; or
X is N;
Y is NHR8 and
Z is O, S or S(xe2x95x90O);
R1 is C1-C4alkyl;
R2 is H, C1-C4alkyl, halogeno-C1-C4alkyl, C3-C6cycloalkyl, C1-C4alkoxymethyl, C1-C4alkoxy, halogeno-C1-C4alkoxy, C1-C4alkylthio, halogeno-C1-C4alkylthio or CN;
R3 and R4 independently of one another are H, C1-C4alkyl, C1-C4alkoxy, OH, CN, NO2, a (C1-C4alkyl)3xe2x80x94Si group, where the alkyl groups can be identical or different, halogen, (C1-C4alkyl)S(xe2x95x90O)m, (halogeno-C1-C4alkyl)S(xe2x95x90O)m, halogeno-C1-C4alkyl or halogeno-C1-C4alkoxy;
R8 is H or C1-C4alkyl;
R9 is methyl, fluoromethyl or difluoromethyl;
m is 0, 1 or 2;
G is O or S; and
A is a direct bond, C1-C10alkylene, xe2x80x94C(xe2x95x90O)xe2x80x94, xe2x80x94C(xe2x95x90S)xe2x80x94 or halogeno-C1-C10alkylene and
R7 is a radical R10; or
A is C1-C10alkylene, xe2x80x94C(xe2x95x90O)xe2x80x94, xe2x80x94C(xe2x95x90S)xe2x80x94 or halogeno-C1-C10alkylene and
R7 is xe2x80x94CN, OR10, N(R10)2, where the radicals R10 can be identical or different, or xe2x80x94S(xe2x95x90O)pR10;
R is an unsubstituted or mono- or polysubstituted C1-C4alkyl-, C2-C4alkenyl-, C2-C4alkynyl-, C3-C6cycloalkyl-, benzyl-, aryl or heteroaryl-group, where the substituents of the groups independently of one another are chosen from the group consisting of halogen, C1-C6alkyl, halogeno-C1-C6alkyl, C3-C6cycloalkyl, halogeno-C3-C6cycloalkyl, C1-C6alkoxy, halogeno-C1-C6alkoxy, C1-C6alkylthio, halogeno-C1-C6alkylthio, phenoxy, CN and nitro, or a phenyl radical which is monosubstituted on two adjacent C atoms by an unsubstituted or mono- to tetrasubstituted C1-C4alkylenedioxy group, where the substituents are selected from the group consisting of C1-C4alkyl and halogen; or CH2Si(C1-C4alkyl)3, where the alkyl groups can be identical or different; and
R5 is C1-C6alkyl, halogeno-C1-C6alkyl, C3-C6cycloalkyl, halogeno-C3-C6cycloalkyl, C1-C6alkoxy, halogeno-C1-C6alkoxy, C1-C6alkylthio, halogeno-C1-C6alkylthio, C1-C6alkylsulfinyl, halogeno-C1-C6alkylsulfinyl, C1-C6alkylsulfonyl, halogeno-C1-C6alkylsulfonyl, C1-C6alkylsulfonyloxy, halogeno-C1-C6alkylsulfonyloxy, C1-C6alkoxy-C1-C6alkyl, halogeno-C1-C6alkoxy-C1-C6alkyl, C1-C6alkylthio-C1-C6alkyl, halogeno-C1-C6alkylthio-C1-C6alkyl, C1-C6alkylsulfinyl-C1-C6alkyl, halogeno-C1-C6alkylsulfinyl-C1-C6alkyl, C1-C6alkylsulfonyl-C1-C6alkyl, halogeno-C1-C6alkylsulfonyl-C1-C6alkyl, C1-C6alkylcarbonyl, halogeno-C1-C6alkylcarbonyl, C1-C6alkoxycarbonyl, halogeno-C1-C6alkoxycarbonyl, C1-C6alkylaminocarbonyl, C1-C4alkoxyiminomethyl, di(C1-C6alkyl)aminocarbonyl, where the alkyl groups can be identical or different; C1-C6alkylaminothiocarbonyl, di(C1-C6alkyl)aminothiocarbonyl, where the alkyl groups can be identical or different; C1-C6alkylamino, di(C1-C6alkyl)amino, where the alkyl groups can be identical or different; halogen, NO2, CN, SF5, thioamido, thiocyanatomethyl, trimethylsilyl; an unsubstituted or mono- to tetrasubstituted C1-C4alkylenedioxy group, where the substituents are chosen from the group consisting of C1-C4alkyl and halogen; aryl-Q-C1-C6alkyl, aryl-Q-C2-C6alkenyl, heterocyclyl-Q-C1-C6alkyl, heterocyclyl-Q-C2-C6alkenyl, or aryl-Q-C1-C6alkyl, aryl-Q-C2-C6alkenyl, heterocyclyl-Q-C1-C6alkyl or heterocyclyl-Q-C2-C6alkenyl which are mono- to pentasubstituted in the aryl or heterocyclyl ring, depending on the possibility of substitution, where the substituents independently of one another are chosen from the group consisting of halogen, C1-C6alkyl, halogeno-C1-C6alkyl, C3-C6cycloalkyl, halogeno-C3-C6cycloalkyl, C1-C6alkoxy, halogeno-C1-C6alkoxy, CN, nitro, OC(xe2x95x90O)-C1-C6alkyl, OH, NH2 and C1-C6alkoxycarbonyl;
where, if q is greater than 1, the radicals R5 can be identical or different;
Q is a direct bond, xe2x80x94CH(OH)xe2x80x94, xe2x80x94C(xe2x95x90O)xe2x80x94 or xe2x80x94S(xe2x95x90O)vxe2x80x94;
v is 0, 1 or 2;
R10 is H, C1-C6alkyl, C2-C8alkenyl, C2-C8alkynyl, C3-C6cycloalkyl; or C1-C6alkenyl, C2-C8alkynyl or C3-C6cycloalkyl-, which are mono- or polysubstituted by substituents from the group consisting of halogen; xe2x80x94Si(C1-C4alkyl)3, where the alkyl groups can be identical or different; C1-C6alkoxycarbonyl, or an aryl or heterocyclyl group which are unsubstituted or mono- or polysubstituted by substituents from the group consisting of halogen, C1-C4alkyl and halogeno-C1-C4alkyl, and
p is 0, 1 or 2; and
(B) either
(I) n is 1 or 2 and q is 1, 2, 3 or, when n 1 is, 4; and A, G, X, Y, Z, R, R2, R3, R4, R5, R7 and R9 are as defined above under (A); or
(II) n is 0;
q is 2,3,4 or 5; and
A, X, Y, Z, R2, R3, R4, R5, R7 and R9 are as defined above under (A); and the radicals R5 can be identical or different; with the proviso that if q is 2, (R5)2 is not dichloro or dimethyl, and with the further proviso that R2 is not CH3 if AR7 is CH3 and (R5)2 is 3-fluoro, 5-CF3 or, together, 3,4-methylenedioxy and R3 R4 are H ; or
(III) n is 0;
q is 1;
A, X, Y, Z, R2, R3, R4, R7 and R9 are as defined above under (A); and
R5 is tert-butyl, C5-C6alkyl, halogeno-C1-C6alkyl, with the exception of CF3; C3-C6cycloalkyl, halogeno-C3-C6cycloalkyl, C5-C6alkoxy, halogeno-C3-C6alkoxy, C2-C6alkylthio, halogeno-C1-C6alkylthio, C1-C6alkylsulfinyl, halogeno-C1-C6alkylsulfinyl, C2-C6alkylsulfonyl, halogeno-C1-C6alkylsulfonyl, C1-C6alkylsulfonyloxy, halogeno-C1-C6alkylsulfonyloxy, C1-C6alkoxy-C1-C6alkyl, halogeno-C1-C6alkoxy-C1-C6alkyl, C1-C6alkylthio-C1-C6alkyl, halogeno-C1-C6alkylthio-C1-C6alkyl, C1-C6alkylsulfinyl-C1-C6alkyl, halogeno-C1-C6alkylsulfinyl-C1-C6alkyl, C1-C6alkylsulfonyl-C1-C6alkyl, halogeno-C1-C6alkylsulfonyl-C1-C6alkyl, C1-C6alkylcarbonyl, halogeno-C1-C6alkylcarbonyl, C2-C6alkoxycarbonyl, halogeno-C1-C6alkoxycarbonyl, C2-C6alkylaminocarbonyl, C1-C4alkoxyiminomethyl, di(C2-C6alkyl)aminocarbonyl, where the alkyl groups can be identical or different; C1-C6alkylaminothio-carbonyl, di(C1-C6alkyl)aminothiocarbonyl, where the alkyl groups can be identical or different; C2-C6alkylamino, di(C2-C6alkyl)amino, where the alkyl groups can be identical or different; SF5, thiocyanatomethyl, trimethylsilyl, aryl-Q-C1-C6alkyl, aryl-Q-C2-C6alkenyl, heterocyclyl-Q-C1-C6alkyl, heterocyclyl-Q-C2-C6alkenyl; or aryl-Q-C1-C6alkyl, aryl-Q-C2-C6alkenyl, heterocyclyl-Q-C1-C6alkyl or heterocyclyl-Q-C2-C6alkenyl which are mono- to pentasubstituted in the aryl or heterocyclyl ring, depending on the possibility of substitution, where the substituents independently of one another are chosen from the group consisting of halogen, C1-C6alkyl, halogeno-C1-C6alkyl, C3-C6cycloalkyl, halogeno-C3-C6cycloalkyl, C1-C6alkoxy, halogeno-C1-C6alkoxy, CN, nitro and C1-C6alkoxycarbonyl;
Q is a direct bond, xe2x80x94CH(OH)xe2x80x94, xe2x80x94C(xe2x95x90O)xe2x80x94 or xe2x80x94S(xe2x95x90O)vxe2x80x94;
v is 0, 1 or 2; or
(IV) n is 1 and
q is 0;
A, X, Y, Z, R2, R3, R4, R7 and R9 are as defined above under (A);
G is O; and
R is n-propyl, n-butyl, sec-butyl, isobutyl, C3-C6cycloalkyl, C3-C6cycloalkyl-C1-C4alkyl, halogeno-C4-C6cycloalkyl-C1-C4alkyl, C1-C4alkylenyl-C3-C6cycloalkyl, C1-C4alkylenyl-halogeno-C3-C6cycloalkyl, CH2Si(C1-C4alkyl)3, where the alkyl groups can be identical or different; a substituted aryl or benzyl, where the substituents of the aryl or benzyl independently of one another are chosen from the group consisting of C1-C6alkyl, halogeno-C1-C6alkyl, C3-C6cycloalkyl, halogeno-C3-C6-cycloalkyl, C1-C6alkoxy, halogeno-C1-C6alkoxy, C1-C6alkylthio, halogeno-C1-C6alkylthio, phenoxy, CN and nitro; or a phenyl radical which is monosubstituted on two adjacent C atoms by an unsubstituted or mono- to tetrasubstituted C1-C4alkylenedioxy group, where the substituents are selected from the group consisting of C1-C4alkyl and halogen;
with the proviso that OR is not n-propyloxy or xe2x80x94OCH2Si(CH3)3 in the 4-position if X is CH, Y is OCH3, Z is O, AR7 is CH3, R2 is CH3 and R3 and R4 are H;
and with the further proviso that R is not phenyl which is substituted by fluorine or chlorine in the 4-position or benzyl which is substituted by methyl or methoxy in the 4-position or monosubstituted by fluorine, chlorine, bromine or CF3 in the 2-, 3- or 4-position if OR is in the p-position, AR7 is CH3, R2 is CH3 and R3 and R4 are H; or
(V) n is 1;
q is 0;
A, X, Y, Z, R, R2, R3, R4, R7 and R9 are as defined above under (A); and
G is S;
with the proviso that R is not methyl if R2 is methyl; or
(VI) n is 1;
q is 0;
A, G, X, Y, Z, R2, R3, R4 and R9 are as defined above under (A);
A is a direct bond, C7-C10alkylene, xe2x80x94C(xe2x95x90O)xe2x80x94, xe2x80x94C(xe2x95x90S)xe2x80x94 or halogeno-C1-C10alkylene and R7 is a radical R10; or
A is C1-C10alkylene, xe2x80x94C(xe2x95x90O)xe2x80x94, xe2x80x94C(xe2x95x90S)xe2x80x94 or halogenoxe2x80x94C1-C10alkylene; and
R7 is CN, O(C1-C4alkyl)2, or N(C1-C4alkyl)2, in which the two alkyl radicals can be identical or different, OR10, N(R10)2, where the radicals R10 can be identical or different, or xe2x80x94S(xe2x95x90Op)R10;
R10 is H; or C5-C8alkenyl, C4-C8alkynyl, C3-C6cycloalkyl; or C1-C6alkyl, C2-C8alkenyl, C2-C8alkynyl or C3-C6cycloalkyl which are mono- or polysubstituted by substituents from the group consisting of halogen; xe2x80x94Si(C1-C4alkyl)3, where the alkyl groups can be identical or different; C1-C6alkoxycarbonyl, or an aryl or heterocyclyl group which are unsubstituted or mono- or polysubstituted by substituents from the group consisting of halogen, C1-C4alkyl and halogeno-C1-C4alkyl; and
R is methyl, ethyl, t-butyl, or mono- or polysubstituted methyl, ethyl or t-butyl, where the substituents independently of one another are chosen from the group consisting of halogen, C1-C6alkyl, halogeno-C1-C6alkyl, C3-C6cycloalkyl, halogeno-C3-C6cycloalkyl, C1-C6alkoxy, halogeno-C1-C6alkoxy, C1-C6alkylthio, halogeno-C1-C6alkylthio, phenoxy, CN and nitro; or a phenyl radical which is monosubstituted on two adjacent C atoms by an unsubstituted or mono- to tetrasubstituted C1-C4alkylenedioxy group, where the substituents are selected from the group consisting of C1-C4alkyl and halogen; or CH2Si(C1-C4alkyl)3, where the alkyl groups can be identical or different; or
(VII) n is 1;
q is 0;
A, G, X, Y, Z, R2, R3, R4, R7 and R9 are as defined above under (A); and
R is C2-C4alkenyl or C2-C4alkynyl which are substituted or unsubstituted, and where the substituents independently of one another are chosen from the group consisting of halogen, C1-C6alkyl, halogeno-C1-C6alkyl, C3-C6cycloalkyl, halogeno-C3-C6cycloalkyl, C1-C6alkoxy, halogeno-C1-C6alkoxy, C1-C6alkylthio, halogeno-C1-C6alkylthio, phenoxy, CN and nitro, with the proviso that AR7 is not methyl if R2 is methyl, R3 and R4 are H and G is oxygen;
and, where appropriate, their possible E/Z isomers, E/Z isomer mixtures and/or tautomers, in each case in the free form or in salt form, a process for the preparation and the use of these compounds, E/Z isomers and tautomers, pesticides, the active compound of which is chosen from these compounds, E/Z isomers and tautomers, and a process for the preparation and the use of these agents, intermediate products, and, where appropriate, their possible E/Z isomers, E/Z isomer mixtures and/or tautomers, in the free form or in salt form, for the preparation of these compounds, where appropriate tautomers, in the free form or in salt form, of these intermediate products and a process for the preparation and the use of these intermediate products and their tautomers.
A preferred compound of the formula (I) is that in which either
X is CH or N,Y is OR, and Z is O, or
X is N, Y is NHR8 and Z is O, S or S(xe2x95x90O);
R1 is C1-C4alkyl;
R2 is H, C1-C4alkyl, halogeno-C1-C4alkyl, C3-C6cycloalkyl, C1-C4alkoxymethyl, C1-C4alkoxy, halogeno-C1-C4alkoxy, C1-C4alkylthio, halogeno-C1-C4alkylthio or CN;
R3 and R4 independently of one another are H, C1-C4alkyl, C1-C4alkoxy, OH, CN, NO2, a (C1-C4alkyl)3xe2x80x94Si group, where the alkyl groups can be identical or different, halogen, (C1-C4alkyl)S(xe2x95x90O)m, (halogeno-C1-C4alkyl)S(xe2x95x90O)m, halogeno-C1-C4alkyl or halogeno-C1-C4alkoxy;
R8 is H or C1-C4alkyl;
R9 is methyl, fluoromethyl or difluoromethyl;
m is 0, 1 or 2; n is 0 or 1; q is 0, 1, 2, 3 or 4 or, if n is 0, 5; either
A is a direct bond, C1-C10alkylene, xe2x80x94C(xe2x95x90O)xe2x80x94, xe2x80x94C(xe2x95x90S)xe2x80x94 or halogeno-C1-C10alkylene and
R7 is a radical R10; or
A is C1-C10alkylene, xe2x80x94C(xe2x95x90O)xe2x80x94, xe2x80x94C(xe2x95x90S)xe2x80x94 or halogeno-C1-C10alkylene and
R7 is xe2x80x94CN, OR10, N(R10)2, where the radicals R10 can be identical or different, or xe2x80x94S(xe2x95x90Op)R10; preferably OR10, N(R10)2, where the radicals R10 can be identical or different, or xe2x80x94S(xe2x95x90Op)R10;
R is a substituted or unsubstituted C1-C4alkyl or aryl group, where the substituents are chosen from the group consisting of halogen, C1-C6alkyl, halogeno-C1-C6alkyl, C3-C6cycloalkyl, halogeno-C3-C6cycloalkyl, C1-C6alkoxy, halogeno-C1-C6alkoxy, CN and nitro;
R5 is C1-C6alkyl, halogeno-C1-C6alkyl, C3-C6cycloalkyl, halogeno-C3-C6cycloalkyl, C1-C6alkoxy, halogeno-C1-C6alkoxy, C1-C6alkylthio, halogeno-C1-C6alkylthio, C1-C6alkyl-sulfinyl, halogeno-C1-C6alkylsulfinyl, C1-C6alkylsulfonyl, halogeno-C1-C6alkylsulfonyl, C1-C6alkoxy-C1-C6alkyl, halogeno-C1-C6alkoxy-C1-C6alkyl, C1-C6alkylthio-C1-C6alkyl, halogeno-C1-C6alkylthio-C1-C6alkyl, C1-C6alkylsulfinyl-C1-C6akyl, halogeno-C1-C6alkylsulfinyl-C1-C6alkyl, C1-C6alkylsulfonyl-C1-C6alkyl, halogeno-C1-C6alkylsulfonyl-C1-C6alkyl, C1-C6alkylcarbonyl, halogeno-C1-C6alkylcarbonyl, C1-C6alkoxycarbonyl, halogeno-C1-C6alkoxycarbonyl, C1-C6alkylaminocarbonyl, C1-C4alkoxyiminomethyl, di(C1-C6alkyl)aminocarbonyl, where the alkyl groups can be identical or different; C1-C6alkylaminothiocarbonyl, di(C1-C6alkyl)aminothiocarbonyl, where the alkyl groups can be identical or different, C1-C6alkylamino, di(C1-C6alkyl)amino, where the alkyl groups can be identical or different, halogen, NO2, CN, SF5, thioamido, thiocyanatomethyl, trimethylsilyl or an unsubstituted or mono- to tetrasubstituted C1-C4alkylenedioxy group, where the substituents are chosen from the group consisting of C1-C4alkyl and halogen, and where, if q is greater than 1, the radicals R5 can be identical or different;
R10 is H, C1-C6alkyl which is unsubstituted or mono- or polysubstituted by substituents from the group consisting of halogen, C3-C6cycloalkyl which is unsubstituted or mono- or polysubstituted by substituents from the group consisting of halogen, C2-C8alkenyl which is unsubstituted or mono- or polysubstituted by substituents from the group consisting of halogen, C2-C8alkynyl which is unsubstituted or mono- or polysubstituted by substituents from the group consisting of halogen, xe2x80x94Si(C1-C4alkyl)3, where the alkyl groups can be identical or different, C1-C6alkoxycarbonyl or an aryl or heterocyclyl group which is unsubstituted or mono- or polysubstituted by substituents from the group consisting of halogen, C1-C4alkyl and halogeno-C1-C4alkyl; and
G is O;
p is 0, 1 or 2;
with the proviso that R7 is other than H if A is methylene, and with the further proviso that R7 is other than methyl if A is a direct bond;
or Axe2x80x94R7 is CH3 and either
R5 is halogen, C1-C6alkyl, halogeno-C1-C6alkyl, C3-C6cycloalkyl, halogeno-C3-C6cycloalkyl or Si(C1-C4alkyl)3, where the alkyl groups can be identical or different, and where the radicals R5 are different;
q is 2, 3, 4 or 5; and n is 0; or
R5 is C4-C6alkyl, C3-C6cycloalkyl, halogeno-C3-C6cycloalkyl or Si(C1-C4alkyl)3, where the alkyl groups can be identical or different;
q is 1; and n is 0; or
R is n-propyl, n-butyl, sec-butyl, isobutyl, C1-C4alkylenyl-C3-C6cycloalkyl, C1-C4alkylenyl-halogeno-C3-C6cycloalkyl, CH2Si(C1-C4alkyl)3, where the alkyl groups can be identical or different, or a substituted phenyl or benzyl group, where the substituents are chosen from the group consisting of halogen, C1-C4alkyl and halogeno-C1-C4alkyl;
R5 is halogen;
q is 0, 1, 2, 3 or 4; and n is 1.
A compound of the formula (I) which is furthermore preferred is that in which either
X is CH or N; Y is OR, and Z is O; or
X is N; Y is NHR8 and Z is 0, S or S(xe2x95x90O);
R1 is C1-C4alkyl;
R2 is H, C1-C4alkyl, halogeno-C1-C4alkyl, C3-C6cycloalkyl, C1-C4alkoxymethyl, C1-C4alkoxy, halogeno-C1-C4alkoxy, C1-C4alkylthio, halogeno-C1-C4alkylthio or CN;
R3 and R4 independently of one another are H, C1-C4alkyl, C1-C4alkoxy, OH, CN, NO2, a (C1-C4alkyl)3xe2x80x94Si group, where the alkyl groups can be identical or different, halogen, (C1-C4alkyl)S(xe2x95x90O)m, (halogeno-C1-C4alkyl)S-(xe2x95x90O)m, halogeno-C1-C4alkyl or halogeno-C1-C4alkoxy;
R8 is H or C1-C4alkyl;
R9 is methyl, fluoromethyl or difluoromethyl;
m is 0, 1 or 2; n is 0 or 1; q is 0, 1,2,3,4 or, if n is 0, 5;
G is O; and
(a) A is a direct bond, C1-C10alkylene, xe2x80x94C(xe2x95x90O)xe2x80x94,xe2x80x94C(xe2x95x90S)xe2x80x94 or halogeno-C1-C10alkylene and
R7 is a radical R10; or
(b) A is C1-C10alkylene, xe2x80x94C(xe2x95x90O)xe2x80x94,xe2x80x94C(xe2x95x90S)xe2x80x94 or halogeno-C1-C10alkylene and
R7 is xe2x80x94CN, OR10, N(R10)2, where the radicals R10 can be identical or different, or xe2x80x94S(xe2x95x90Op)R10; and in the groups (I) and (II),
R is an unsubstituted or mono- or polysubstituted C1-C4alkyl, C2-C4alkenyl, C2-C4alkynyl, benzyl or aryl group, where the substituents are chosen from the group consisting of halogen, C1-C6alkyl, halogeno-C1-C6alkyl, C3-C6cycloalkyl, halogeno-C3-C6cycloalkyl, C1-C6alkoxy, halogeno-C1-C6alkoxy, C1-C6alkylthio, halogeno-C1-C6alkylthio, phenoxy, CN and nitro; or CH2Si(C1-C4alkyl)3, where the alkyl groups can be identical or different; or a phenyl radical which is monosubstituted on two adjacent C atoms by a xe2x80x94Oxe2x80x94CH2xe2x80x94Oxe2x80x94 group; and
R5 is C1-C6alkyl, halogeno-C1-C6alkyl, C3-C6cycloalkyl, halogeno-C3-C6cycloalkyl, C1-C6alkoxy, halogeno-C1-C6alkoxy, C1-C6alkylthio, halogeno-C1-C6alkylthio, C1-C6alkylsulfinyl, halogeno-C1-C6alkylsulfinyl, C1-C6alkylsulfonyl, halogeno-C1-C6alkylsulfonyl, C1-C6alkylsulfonyloxy, halogeno-C1-C6alkylsulfonyloxy, C1-C6alkoxy-C1-C6alkyl, halogeno-C1-C6alkoxy-C1-C6alkyl, C1-C6alkylthio-C-C6alkyl, halogeno-C1-C6alkylthio-C1-C6alkyl, C1-C6alkylsulfinyl-C1-C6alkyl, halogeno-C1-C6alkylsulfinyl-C1-C6alkyl, C1-C6alkylsulfonyl-C1-C6alkyl, halogeno-C1-C6alkylsulfonyl-C1-C6alkyl, C1-C6alkylcarbonyl, halogeno-C1-C6alkylcarbonyl, C1-C6alkoxycarbonyl, halogeno-C1-C6alkoxycarbonyl, C1-C6alkylaminocarbonyl, C1-C4alkoxyiminomethyl, di(C1-C6alkyl)aminocarbonyl, where the alkyl groups can be identical or different, C1-C6alkylaminothiocarbonyl, di(C1-C6alkyl)aminothiocarbonyl, where the alkyl groups can be identical or different, C1-C6alkylamino, di(C1-C6alkyl)amino, where the alkyl groups can be identical or different, halogen, NO2, CN, SF5, thioamido, thiocyanatomethyl, trimethylsilyl, an unsubstituted or mono- to tetrasubstituted C1-C4alkylenedioxy group, where the substituents are chosen from the group consisting of C1-C4alkyl and halogen; aryl-Q-C1-C6alkyl, aryl-Q-C2-C6alkenyl, heterocyclyl-Q-C1-C6alkyl, heterocyclyl-Q-C2-C6alkenyl, or aryl-Q-C1-C6alkyl, aryl-Q-C2-C6alkenyl, heterocyclyl-Q-C1-C6alkyl or heterocyclyl-Q-C2-C6alkenyl which are mono- to pentasubstituted in the aryl or heterocyclyl ring, depending on the possibility of substitution, where the substituents independently of one another are chosen from the group consisting of halogen, C1-C6alkyl, halogeno-C1-C6alkyl, C3-C6cycloalkyl, halogeno-C3-C6-cycloalkyl, C1-C6alkoxy, halogeno-C1-C6alkoxy, CN, nitro and C1-C6alkoxycarbonyl;
and where, if q is greater than 1, the radicals R5 can be identical or different;
Q is a direct bond, xe2x80x94CH(OH)xe2x80x94; xe2x80x94C(xe2x95x90O)xe2x80x94 or xe2x80x94S(xe2x95x90O)vxe2x80x94; preferably a direct bond, xe2x80x94CH(OH)xe2x80x94 or xe2x80x94C(xe2x95x90O)xe2x80x94,
v is 0, 1 or 2;
R10 is H, C1-C6alkyl which is unsubstituted or mono- or polysubstituted by substituents from the group consisting of halogen, C3-C6cycloalkyl which is unsubstituted or mono- or polysubstituted by substituents from the group consisting of halogen, C2-C8alkenyl which is unsubstituted or mono- or polysubstituted by substituents from the group consisting of halogen, C2-C8alkynyl which is unsubstituted or mono- or polysubstituted by substituents from the group consisting of halogen, xe2x80x94Si(C1-C4alkyl)3, where the alkyl groups can be identical or different, C1-C6alkoxycarbonyl or an aryl or heterocyclyl group which is unsubstituted or mono- or polysubstituted by substituents from the group consisting of halogen, C1-C4alkyl and halogeno-C1-C4alkyl, and
p is 0, 1 or 2;
with the proviso that Axe2x80x94R7 is other than CH3; or
Axe2x80x94R7 in the following groups (c) to (k) is CH3 and X, Y, Z, R1, R2, R3, R4, R8, R9 and m are a defined above under (C), and either
(c) R5 is halogen, C1-C6alkyl, halogeno-C1-C6alkyl, C3-C6cycloalkyl, halogeno-C3-C6cycloalkyl or Si(C1-C4alkyl)3, where the alkyl groups can be identical or different, and where the radicals R5 are different;
q is 2, 3, 4 or 5; and n is 0; or
(d) R5 is C4-C6alkyl, C3-C6cycloalkyl, halogeno-C3-C6cycloalkyl or Si(C1-C4alkyl)3, the alkyl groups can be identical or different;
q is 1; and n is 0; or
(e) R is n-propyl, n-butyl, sec-butyl, isobutyl, C3-C6cycloalkyl, C3-C6cycloalkyl-C1-C4alkyl, halogeno-C3-C6cycloalkyl-C1-C4alkyl, C1-C4alkylenyl-C3-C6cycloalkyl, C1-C4alkyl halogeno-C3-C6cycloalkyl, CH2Si(C1-C4alkyl)3, where the alkyl groups can be identical or different, or a substituted phenyl or benzyl group, where the substituents are chosen from the group consisting of halogen, C1-C4alkyl and halogeno-C1-C4alkyl;
R5 is halogen;
q is 0, 1, 2, 3 or 4; and n is 1;
with the proviso that OR is not m-CF3-benzyloxy in the p-position if X is CH, Y is OCH3, Z is O, R2 is CH3, R3 and R4 are hydrogen, R9 is CH3, n is 1 and q is 0; or
(f) R is an unsubstituted or mono- or polysubstituted C1-C4alkyl, C2-C4alkenyl, C2-C4alkynyl, benzyl or aryl group, where the substituents are chosen from the group consisting of halogen, C1-C6alkyl, halogeno-C1-C6alkyl, C3-C6cycloalkyl, halogeno-C3-C6cycloalkyl, C1-C6alkoxy, halogeno-C1-C6alkoxy, C1-C6alkylthio, halogeno-C1-C6alkylthio, CN and nitro; or xe2x80x94CH2Si(C1-C4alkyl)3, where the alkyl groups can be identical or different; or a phenyl radical which is monosubstituted on to two adjacent C atoms by a xe2x80x94Oxe2x80x94CH2xe2x80x94Oxe2x80x94 group;
R5 is aryl-Q-C1-C6alkyl, aryl-Q-C1-C6alkenyl, heterocyclyl-Q-C1-C6alkyl, heterocyclyl-Q-C2-C6alkenyl, or aryl-Q-C1-C6alkyl, aryl-Q-C2-C6alkenyl, hetero-cyclyl-Q-C1-C6alkyl or heterocyclyl-Q-C2-C6alkenyl which are mono- to pentasubstituted in the aryl or heterocyclyl ring, depending on the possibility of substitution, where the substituents independently of one another are chosen from the group consisting of halogen, C1-C6alkyl, halogeno-C1-C6alkyl, C3-C6cycloalkyl, halogeno-C3-C6cycloalkyl, C1-C6alkoxy, halogeno-C1-C6alkoxy, CN, nitro and C1-C6alkoxycarbonyl;
where, if q is greater than 1, the radicals R5 can be identical or different;
Q is a direct bond, xe2x80x94CH(OH)xe2x80x94; or xe2x80x94C(xe2x95x90O)xe2x80x94;
q is 1, 2, 3 or 4; and n is 0 or 1, where if
q is 2, 3 or 4, one or more of the radicals R5 also independently of one another can be C1-C6alkyl, halogeno-C1-C6alkyl, C3-C6cycloalkyl, halogeno-C3-C6cycloalkyl, C1-C6alkoxy, halogeno-C1-C6alkoxy, C1-C6alkylthio, halogeno-C1-C6alkylthio, C1-C6alkylsulfinyl, halogeno-C1-C6alkylsulfinyl, C1-C6alkylsulfonyl, halogeno-C1-C6alkylsulfonyl, C1-C6alkoxy-C1-C6alkyl, halogeno-C1-C6alkoxy-C1-C6alkyl, C1-C6alkyithio-C1-C6alkyl, halogeno-C1-C6alkylthio-C1-C6alkyl, C1-C6alkylsulfinyl-C1-C6alkyl, halogeno-C1-C6alkylsulfinyl-C1-C6alkyl, C1-C6alkylsulfonyl-C1-C6alkyl, halogeno-C1-C6alkylsulfonyl-C1-C6alkyl, C1-C6alkylcarbonyl, halogeno-C1-C6alkylcarbonyl, C1-C6alkoxycarbonyl, halogeno-C1-C6alkoxycarbonyl, C1-C6alkylaminocarbonyl, C1-C4alkoxyiminomethyl, di(C1-C6alkyl)aminocarbonyl, where the alkyl groups can be identical or different, C1-C6alkylaminothiocarbonyl, di(C1-C6alkyl)aminothiocarbonyl, where the alkyl groups can be identical or different, C1-C6alkylamino, di(C1-C6alkyl)amino, where the alkyl groups can be identical or different, halogen, NO2, CN, SF5, thioamido, thiocyanatomethyl, trimethylsilyl or a C1-C4alkylenedioxy group which is unsubstituted or mono- to tetrasubstituted, where the substituents are chosen from the group consisting of C1-C4alkyl and halogen; or
(g) R is C3-C6cycloalkyl, halogeno-C3-C6cycloalkyl or an unsubstituted or mono- or poly-substituted phenyl or benzyl group, where the substituents are chosen from the group consisting of halogen, C1-C4alkyl and halogeno-C1-C4alkyl,
R5 is C1-C6alkyl, C1-C6alkoxy, halogeno-C1-C6alkyl or halogeno-C1-C6alkoxy;
q is 1 and n is 1, or
(h) R is C3-C6cycloalkyl-C1-C4alkyl or halogeno-C3-C6cycloalkyl-C1-C4alkyl,
R5 is C1-C6alkyl, C1-C6alkoxy, halogeno-C1-C6alkyl or halogeno-C1-C6alkoxy;
q is 1 and n is 1, or
(i) R is methyl, ethyl, isopropyl or tert-butyl;
R5 is C1-C6alkyl, C1-C6alkoxy, halogeno-C1-C6alkyl, halogeno-C1-C6alkoxy or halogen;
q is 1; and n is 1; or
(k) R is n-propyl;
R5 is C1-C6alkyl or C1-C6alkoxy;
q is 1; and n is 1;
and, where appropriate, its possible E/Z isomers, E/Z isomer mixtures and/or tautomers, in each case in the free form or in salt form.
Certain methoxyacrylic acid derivatives are proposed as active compounds in pesticides in the literature. However, the biological properties of these known compounds are not completely satisfactory in the field of pest control, and for this reason there is the need to provide further compounds having pest control properties, in particular for control of insects and representatives of the order Acarina, and in particular for control of phytopathogenic microorganisms, this object being achieved according to the invention by providing the present compounds of the formula (I).
Some of the compounds of the formula (I) and of the formulae (III), (IV) and (VI) defined below contain asymmetric carbon atoms, which means that the compounds can occur in an optically active form. Because of the presence of the C=X and the oximino double bonds, the compounds can occur in the E and Z isomer forms. Atropisomers of the compounds can furthermore occur. The formulae (I), (III), (IV) and (VI) are intended to include all these possible isomeric forms and mixtures thereof, for example racemates or E/Z isomer mixtures, and, where appropriate, the salts thereof, even though this is not mentioned specifically each time.
Unless defined otherwise, the general terms used above and below are as defined below.
Unless defined otherwise, carbon-containing groups and compounds in each case contain 1 up to and including 8, preferably 1 up to and including 6, in particular 1 up to and including 4, especially 1 or 2, carbon atoms.
Alkylxe2x80x94as a group per se and as a structural element of other groups and compounds, such as of halogenoalkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylcarbonyl, alkoxy-carbonyl, alkylamino, alkoxyiminomethyl, alkylaminocarbonyl and alkylaminothiocarbonylxe2x80x94is, in each case under due consideration of the number, embraced from case to case, of the carbon atoms contained in the corresponding group or compound, either straight-chain, i.e. methyl, ethyl, propyl, butyl, pentyl or hexyl, or branched, for example isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl or isohexyl.
Alkenylxe2x80x94as a group per se and as a structural element of other groups and compounds, such as of halogenoalkenylxe2x80x94is, in each case under due consideration of the number, embraced from case to case, of the carbon atoms contained in the corresponding group or compound, either straight-chain, for example vinyl, 1-methylvinyl, allyl, 1-butenyl or 2-hexenyl, or branched, for example isopropenyl.
Alkynylxe2x80x94as a group per se and as a structural element of other groups and compounds, such as of halogenoalkynylxe2x80x94is, in each case under due consideration of the number, embraced from case to case, of the carbon atoms contained in the corresponding group or compound, either straight-chain, for example propargyl, 2-butinyl or 5-hexinyl, or branched, for example 2-ethinylpropyl or 2-propargylisopropyl.
C3-C6cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
Alkylenexe2x80x94as a group per se and as a structural element of other groups and compounds, such as of halogenoalkylenexe2x80x94is, in each case under due consideration of the number, embraced from case to case, of carbon atoms contained in the corresponding group or compound, either straight-chain, for example xe2x80x94CH2CH2xe2x80x94, xe2x80x94CH2CH2CH2xe2x80x94 or xe2x80x94CH2CH2CH2CH2xe2x80x94, or branched, for example xe2x80x94CH(CH3)xe2x80x94, xe2x80x94CH(C2H5)xe2x80x94, xe2x80x94C(CH3)2xe2x80x94, xe2x80x94CH(CH3)CH2xe2x80x94 or xe2x80x94CH(CH3)CH(CH3)xe2x80x94.
Aryl is phenyl or naphthyl, in particular phenyl.
Heterocyclyl is a 5- to 7-membered aromatic or non-aromatic ring having 1 to 3 hetero-atoms, which are chosen from the group consisting of N, O and S. Aromatic 5- and 6-membered rings which contain a nitrogen atom as the heteroatom and if appropriate a further heteroatom, preferably nitrogen or sulfur, in particular nitrogen, are preferred. Preferred heteroaryl radicals in the radical R5 are -pyrazinyl, -pyrid-3xe2x80x2-yl, -pyrid-2xe2x80x2-yl, -pyrid-4xe2x80x2-yl, -pyrimidin-2xe2x80x2-yl, -pyrimidin-4xe2x80x2-yl, -pyrimidin-5xe2x80x2-yl, -thiazol-2xe2x80x2-yl, -oxazol-2xe2x80x2-yl, -thien-2xe2x80x2-yl, -thien-3xe2x80x2-yl and -thiazol-2xe2x80x2-yl.
Halogenxe2x80x94as a group per se and as a structural element of other groups and compounds, such as of halogenoalkyl, halogenoalkenyl and halogenoalkynylxe2x80x94is fluorine, chlorine, bromine or iodine, in particular fluorine, chlorine or bromine, especially fluorine or chlorine, and very particularly fluorine.
Halogen-substituted carbon-containing groups and compounds, such as halogenoalkyl, halogenoalkenyl or halogenoalkynyl, can be partly halogenated or perhalogenated, and in the case of polyhalogenation, the halogen substituents can be identical or different. Examples of halogenoalkylxe2x80x94as a group per se and as a structural element of other groups and compounds, such as of halogenoalkenylxe2x80x94are methyl which is mono- to trisubstituted by fluorine, chlorine and/or bromine, such as CHF2 or CF3; ethyl which is mono- to penta-substituted by fluorine, chlorine and/or bromine, such as CH2CF3, CF2CF3, CF2CC3, CF2CHCl2, CF2CHF2, CF2CFCl2, CF2CHBr2, CF2CHClF, CF2CHBrF or CCIFCHClF; propyl or isopropyl which is mono- to heptasubstituted by fluorine, chlorine and/or bromine, such as CH2CHBrCH2Br, CF2CHFCF3, CH2CF2CF3 or CH(CF3)2; and butyl or one of its isomers which is mono- to nonasubstituted by fluorine, chlorine and/or bromine, such as CF(CF3)CHFCF3 or CH2(CF2)2CF3. Halogenoalkenyl is, for example, CH2CHxe2x95x90CHCl, CH2CHxe2x95x90CCl2, CH2CFxe2x95x90CF2 or CH2CHxe2x95x90CHCH2Br. Halogenoalkynyl is, for example, CH2Cxe2x89xa1CF, CH2Cxe2x89xa1CCH2Cl or CF2CF2Cxe2x89xa1CCH2F.
Some compounds of the formula (I) and of the formulae (III), (IV) and (VI) defined below can, as is familiar to the expert, exist as tautomers, in particular if R7 is H. The compounds of the formulae (I), (III), (IV) and (VI) above and below are therefore to be understood as also meaning corresponding tautomers, although the latter are not mentioned specifically in each case.
Compounds of the formula (I) and of the formulae (III), (IV) and (VI) defined below which have at least one basic centre can form, for example, acid addition salts. These are formed, for example, with strong inorganic acids, such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrous acid, a phosphoric acid or a hydrogen halide acid, with strong organic carboxylic acids, such as C1-C4alkanecarboxylic acids which are unsubstituted or substituted, for example by halogen, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic, malonic, succinic, maleic, fumaric or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic, lactic, malic, tartaric or citric acid, or such as benzoic acid, or with organic sulfonic acids, such as C1-C4alkane- or arylsulfonic acids which are unsubstituted or substituted, for example by halogen, for example methane- or p-toluenesulfonic acid. Compounds of the formula (I) with at least one acid group can furthermore form salts with bases. Suitable salts with bases are, for example, metal salts, such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, for example ethyl-, diethyl-, triethyl- or dimethylpropylamine, or a mono-, di- or trihydroxy-lower alkylamine, for example mono-, di- or triethanolamine. Where appropriate, corresponding inner salts can furthermore be formed. Agrochemically advantageous salts are preferred in the context of the invention; However, the invention also relates to salts which have disadvantages for agrochemical uses, for example salts which are toxic to bees or fish, which are employed, for example, for isolation or purification of free compounds of the formula (I) or agrochemically usable salts thereof. As a result of the close relationship between the compounds of the formula (I) in the free form and in the form of their salts, free compounds of the formula (I) or their salts above and below are accordingly and appropriately also to be understood as meaning the corresponding salts or, respectively, free compounds of the formula (I), where appropriate. The same applies to tautomers of compounds of the formulae (I), (III), (IV) and (VI) and salts thereof. In general, in each case the free form is preferred.
Preferred embodiments in the context of the inventionxe2x80x94in each case taking into consideration the above provisosxe2x80x94are:
(1) a compound of the formula (I) in which X is CH;
(2) a compound of the formula (I), in which Y is OR1, preferably C1-C2alkoxy, in particular methoxy;
(3) a compound of the formula (I), in which Z is O;
(4) a compound of the formula (I), in which R1 is C1-C2alkyl;
(5) a compound of the formula (I), in which R2 is H, C1-C4alkyl, halogeno-C1-C4alkyl or C3-C6cycloalkyl, preferably C1-C4alkyl or halogeno-C1-C4alkyl, in particular C1-C2alkyl especially methyl;
(6) a compound of the formula (I), in which R3 is H, C1-C4alkyl, C1-C4alkoxy, OH, CN, NO2, halogen, halogeno-C1-C4alkyl or halogeno-C1-C4alkoxy, preferably H, C1-C4alkyl, C1-C4alkoxy or halogen, in particular H, methyl, methoxy, chlorine or fluorine, especially H;
(7) a compound of the formula (I), in which R4is H, C1-C4alkyl, C1-C4alkoxy, OH, CN, NO2, halogen, halogeno-C1-C4alkyl or halogeno-C1-C4alkoxy, preferably H, C1-C4alkyl, C1-C4alkoxy or halogen, in particular H, methyl, methoxy, chlorine or fluorine, especially H;
(8) a compound of the formula (I), in which R8 is H or C1-C2alkyl, preferably C1-C2alkyl, in particular methyl;
(9) a compound of the formula (I), in which R9 is methyl or fluoromethyl, preferably methyl;
(10) a compound of the formula (I), in which m is 0 or 2, preferably 2;
(11) a compound of the formula (I), in which n is 1 or 2, preferably 1;
(12) a compound of the formula (I), in which n is 1 and q is 0;
(13) a compound of the formula (I), in which AR7 is ethyl, n is 1 and q is 0;
(14) a compound of the formula (I), in which AR7 is methyl, n is 0 and q is 2.
(15) a compound of the formula (I), in which G is oxygen;
(16) a compound of the formula (I), in which n is 1 and q is 1 or 2; preferably and n is 1 q is 1;
(17) a compound of the formula (I), in which A is a direct bond, C1-C10alkylene, or halogeno-C1-C10alkylene, preferably a direct bond or C1-C4alkylene, in particular a direct bond or methylene, and R7 is a radical R10;
(18) a compound of the formula (I), in which AR7is C1-C4alkyl, C3alkenyl, which is optionally substituted with chlorine; or C3alkenyl; preferably methyl or ethyl; in particular ethyl; in particular methyl;
(19) n is 1, q is 0, and R is a substituted aryl- or benzyl-group, where the substituents are chosen from the group consisting of halogen, C1-C4alkyl, halogeno-C1-C4alkyl, C3-C6cycloalkyl and halogeno-C3-C6cycloalkyl, or CH2Si(CH3)3, preferably a substituted phenyl or benzyl group, where the substituents are chosen from the group consisting of halogen, C1-C4alkyl and halogeno-C1-C4alkoxy, in particular halogen, methyl and halogenomethyl, especially chlorine and trifluoromethyl;
(20) a compound of the formula (I), in which n is 1, q is 0 and OR is in the para-position;
(21) a compound of the formula (I), in which A is a direct bond, C1-C10alkylene, or halogeno-C1-C10alkylene, preferably a direct bond or C1-C4alkylene, in particular a direct bond or methylene; and
R7 is C1-C4alkyl which is unsubstituted or mono- to trisubstituted by substituents from the group consisting of hydrogen, C3-C6cycloalkyl which is unsubstituted or mono- or disubstituted by substituents from the group consisting of halogen, C2-C4alkenyl which is unsubstituted or mono- or trisubstituted by substituents from the group consisting of halogen, C2-C4alkynyl which is unsubstituted or mono- or disubstituted by substituents from the group consisting of halogen, xe2x80x94Si(CH3)3, C1-C4alkoxycarbonyl, or an aryl group which is unsubstituted or mono- or disubstituted by substituents from the group consisting of halogen, C1-C4alkyl and halogeno-C1-C4alkyl, preferably unsubstituted C1-C4alkyl, cyclopropyl which is disubstituted by substituents from the group consisting of halogen, C2-C3alkenyl which is disubstituted by substituents from the group consisting of halogen, unsubstituted C2-C3alkynyl, xe2x80x94Si(CH3)3, C1-C4alkoxycarbonyl, or a phenyl group which is monosubstituted by substituents from the group consisting of halogen, C1-C2alkyl and halogeno-C1-C4alkyl, in particular unsubstituted C1-C3alkyl, cyclopropyl which is disubstituted by chlorine, vinyl which is disubstituted by chlorine, acetylenyl, xe2x80x94Si(CH3)3, ethoxycarbonyl or trifluoro-phenyl;
(22) a compound of the formula (I), in which Axe2x80x94R7 is CH3, R5 is halogen, C1-C4alkyl, C1-C4alkoxy, halogeno-C1-C4alkyl, C3-C6cycloalkyl or Si(CH3)3, preferably halogen, C1-C2alkyl or C1-C4alkoxy, in particular chlorine, fluorine, methyl or C1-C3alkoxy; especially fluorine, methyl or C1-C2alkoxy, and where the radicals R5 are in each case identical or different, in particular different; and q is 2 or 3, preferably 2; and n is 0;
(23) a compound of the formula (I), in which Axe2x80x94R7 is CH3, R5 is C3-C6cycloalkyl, halogeno-C3-C6cycloalkyl or Si(CH3)3, preferably C3-C6cycloalkyl or Si(CH3)3, in particular cyclopropyl or Si(CH3)3, and q is 1; and n is 0;
(24) a compound of the formula (I), in which Axe2x80x94R7 is CH3; R is n-propyl, n-butyl, sec-butyl, isobutyl, C3-C6cycloalkyl, C1-C2alkylenyl-halogeno-C3-C6cycloalkyl or CH2Si(CH3)3preferably n-butyl, sec-butyl, isobutyl or cyclopentyl; and n is 1 and q is 0;
(25) a compound of the formula (I), in which X is CH; Y is C1-C2alkoxy; Z is 0; A is a direct bond or methylene; R2 and R9 are methyl; R3 and R4 are H; n is 1; q is 1 or 2; R7 is a radical R10; R is a substituted aryl group, where the substituents are chosen from the group consisting of halogen, methyl and halogenomethyl; and R10 is H, unsubstituted C1-C4alkyl, cyclopropyl which is disubstituted by substituents from the group consisting of halogen, C2-C3alkenyl which is disubstituted by substituents from the group consisting of halogen, unsubstituted C2-C3alkynyl, xe2x80x94Si(CH3)3, C1-C4alkoxycarbonyl, or a phenyl group which is monosubstituted by substituents from the group consisting of halogen, C1-C2alkyl and halogeno-C1-C4alkyl;
(26) a compound of the formula (I), in which X is CH; Y is C1-C2alkoxy; Z is O; R2 and R9 are methyl; R3 and R4 are H; n is 0; q is 2; Axe2x80x94R7 is CH3; and R5 is chlorine, fluorine, methyl, halogenomethyl or C1-C4alkoxy; especially where the radicals R5 are different;
(27) a compound of the formula (I), in which X is CH; Y is C1-C2alkoxy; Z is O; R2 and R9 are methyl; R3 and R4 are H; n is 1; q is 1 or 2; R is a substituted phenyl or benzyl group, where the substituents are chosen from the group consisting of fluorine, chlorine, bromine, methyl and halogenomethyl, and R5 is fluorine or chlorine;
(28) a compound of the formula (I), in which n is 0, q is 1, Q is a direct bond and R5 is phenyl-ethyl, phenyl-ethenyl, heteroaryl-ethyl or heteroaryl-ethenyl, or phenyl-ethyl, phenyl-ethenyl, heteroaryl-ethyl or heteroaryl-ethenyl which is mono- to trisubstituted in the phenyl or heteroaryl ring, depending on the possibility of substitution, where the substituents independently of one another are chosen from the group consisting of fluorine, chlorine, bromine, C1-C2alkyl, halogenomethyl, methoxy, halogenomethoxy and C1-C2alkoxycarbonyl;
(29) a compound of the formula (I), in which Axe2x80x94R7 is methyl or ethyl, R is C3-C6cycloalkyl-CH2xe2x80x94 or halogeno-C3-C6cycloalkyl-CH2xe2x80x94, R5 is C1-C2alkyl, C1-C2alkoxy or halogen and q is 1 and n is 1;
(30) a compound of the formula (I), in which Axe2x80x94R7 is CH3, R is methyl, ethyl, isopropyl or tert-butyl; R5 is C1-C4alkyl, C1-C4alkoxy, fluorine or chlorine; q is 1; and n is 1;
(31) a compound of the formula (I), in which Axe2x80x94R7 is CH3, R is n-propyl; R5 is C1-C4alkyl or C1-C4alkoxy; q is 1; and n is 1;
(32) X is CH; Y is C1-C2alkoxy; Z is O; R2 and R9 are methyl; R3 and R4 are H; n is 1; or 2; R is methylenedichlorocyclopropyl or a substituted phenyl or benzyl group, where the substituents are chosen from the group consisting of fluorine, chlorine, bromine, methyl and halogenomethyl; and R5 is fluorine or chlorine;
(33) AR7 is methyl or ethyl, n is 1, q is 0, and R is CH2Si(CH3)3 or a substituted aryl or benzyl group, where the substituents are chosen from the group consisting of halogen, C1-C4alkyl, halogeno-C1-C4alkyl, C3-C6cycloalkyl and halogeno-C3-C6cycloalkyl.
(36) a compound of the formula: 
xe2x80x83wherein the Cxe2x95x90N double bond marked with E has the E configuration;
(37) (2-{2-[4-(2,2-Dichloro-cyclopropylmethoxy)-3-fluoro-phenyl]-2-methoxyimino-1-methyl-ethylideneaminooxymethyl}phenyl)-3-methoxy-acrylic acid methyl ester (compound 1.3);
(38) Methoxyimino-(2-{2-methoxyimino-1-methyl-2-[4-(3-trifluoromethyl-phenoxy)-phenyl]-ethylideneaminooxymethyl}-phenyl)-acetic acid methyl ester (compound 2.31);
(39) (2-{2-[3,5-Difluoro-4-(3-trifluoromethyl-benzyloxy)-phenyl]-2-methoxyimino-1-methyl-ethylideneaminooxymethyl}-phenyl)-3-methoxy-acrylic acid methyl ester (compound 1.11);
(40) 2-Methoxyimino-2-(2-{2-methoxyimino-1-methyl-2-[4-(3-trifluoromethyl-phenoxy)-phenyl]-ethylideneaminooxymethyl}-phenyl)-N-methyl-acetamide (compound 3.31);
(41) [2-(2-{4-[2-(3,5-Bis-trifluoromethyl-phenyl)-ethyl]-phenyl}-2-methoxyimino-1-methylideneaminooxymethyl)-phenyl]-3-methoxy-acrylic acid methyl ester (compound 155.6);
(42) 3-Methoxy-2-[2-(2-methoxyimino-1-methyl-2-{4-[2-(3-trifluoromethyl-phenyl)-ethyl]-phenyl}-ethylideneaminooxymethyl)-phenyl]-acrylic acid methyl ester (compound 155.7);
(43) (2-{2-[4-(2,2-Dichloro-cyclopropylmethoxy)-2,5-difluoro-phenyl]-2-methoxyimino-1-methyl-ethylideneaminooxymethyl}-phenyl)-3-methoxy-acrylic acid methyl ester (compound 1.13);
(44) (2-{2-[2,5-Difluoro-4-(3-trifluoromethyl-benzyloxy)-phenyl]-2-methoxyimino-1-methyl-ethylideneaminooxymethyl}-phenyl)-3-methoxy-acrylic acid methyl ester (compound 1.14);
(45) 3-Methoxy-2-[2-(1-{methoxyimino-[4-(3-trifluoromethyl-benzyloxy)-phenyl]-methyl}-propylideneaminooxymethyl)-phenyl]-acrylic acid methyl ester (compound 1.25);
(46) [2-(1-{[4-(4-Fluoro-benzyloxy)-phenyl]-methoxyimino-methyl}-propylideneaminooxymethyl)-phenyl]-3-methoxy-acrylic acid methyl ester (compound 1.66)
(47) [2-(2-{4-[2-(2,4-Dichloro-phenyl)-ethyl]-phenyl}-2-methoxyimino-1-methyl-ethyldeneaminooxymethyl)-phenyl]-3-methoxy-acrylic acid methyl ester (compound 155.3);
(48) (2-{2-[4-(4-Bromo-phenoxy)-phenyl]-2-methoxyimino-1-methyl-ethylideneaminooxymethyl}-phenyl)-3-methoxy-acrylic acid methyl ester (compound 1.41);
(49) (2-{2-[2-Fluoro-4-(3-trifluoromethyl-benzyloxy)-phenyl]-2-methoxyimino-1-methyl-ethylideneaminooxymethyl}-phenyl)-3-methoxy-acrylic acid methyl ester (compound 1.7);
(50) (2-{2-Allyloxyimino-1-methyl-2-[4-(3-trifluoromethyl-benzyloxy)-phenyl]-ethylideneaminooxymethyl)phenyl)-3-methoxy-acrylic acid methyl ester (compound 4.4);
(51) (2-{2-Ethoxyimino-1-methyl-2-[4-(3-trifluoromethyl-benzyloxy)-phenyl]-ethylideneaminooxymethyl}-phenyl-3-methoxy-acrylic acid methyl ester (compound 4.5);
(52) 3-Methoxy-2-(2-{1-methyl-2-prop-2-ynyloxyimino-2-[4-(3-trifluoromethyl-benzyloxy)-phenyl]-ethylideneaminooxymethyl}-phenyl)-acrylic acid methyl ester (compound 4.6);
(53) (2-{2-[4-(2,2-Dichloro-cyclopropylmethoxy)-2-fluoro-phenyl]-2-methoxyimino-1-methyl-ethylideneaminooxymethyl)-phenyl)-3-methoxy-acrylic acid methyl ester (compound 1.9);
(54) {2-[4-(4-Bromo-phenoxy)-phenyl]-2-methoxyimino-1-methyl-ethylideneaminooxymethyl}-phenyl)-methoxyimino-acetic acid methyl ester (compound 2.28);
(55) (2-{2-[4-(3-Chloro-phenoxy)-phenyl]-2-methoxyimino-1-methyl-ethylidene-aminooxymethyl}-phenyl)-3-methoxy-acrylic acid methyl ester (compound 1.36);
(56) (2-{2-[4-(4-.tert.-Butyl-benzyloxy)-phenyl]-2-methoxyimino-1-methyl-ethylideneaminooxymethyl)-phenyl)-3-methoxy-acrylic acid methyl ester (compound 1.28);
(57) (2-{2-[4-(4-Fluoro-benzyloxy)-phenyl]-1-methyl-2-prop-2-ynyloxyimino-ethylideneaminooxymethylkphenyl)-3-methoxy-acrylic acid methyl ester (compound 4.21);
(58) (2-{2-Ethoxyimino-2-[4-(4-fluoro-benzyloxy)-phenyl]-1-methyl-ethylideneaminooxymethyl}-phenyl)-3-methoxy-acrylic acid methyl ester (compound 4.24);
(59) Methoxyimino-(2-(1-methyl-2-prop-2-ynyloxyimino-2-[4-(3-trifluoromethyl-benzyloxy)-phenyl]-ethylideneaminooxymethyl}-phenyl)-acetic acid methyl ester (compound 4.18);
(60) (2-{2-Butoxylmino-1-methyl-2-[4-(3-trifluoromethyl-benzyloxy)-phenyl]-ethylideneaminooxymethyl}-phenyl)-3-methoxy-acrylic acid methyl ester (compound 4.15);
(61) (2-{2-[4-(4- Chloro-phenoxy)-phenyl]-2-ethoxyimino-1-methyl-ethylideneaminooxymethyl}-phenyl)-3-methoxy-acrylic acid methyl ester (compound 4.20);
(62) {2-[2-(4-Isobutoxy-phenyl)-2-methoxyimino-1-methyl-ethylideneaminooxymethyl]-phenyl}-3-methoxy-acrylic acid methyl ester (compound 1.31);
(63) {2-[2-(2-Fluoro-4-propoxy-phenyl)-2-methoxyimino-1-methyl-ethylideneaminooxymethyl]-phenyl}-3-methoxy-acrylic acid methyl ester (compound 1.63);
(64) (2-{2-Ethoxyimino-1-methyl-2-[4-(4-trifluoromethyl-benzyloxy)-phenyl]-ethylideneaminooxymethyl)phenyl)-3-methoxy-acrylic acid methyl ester (compound 4.25);
(65) (2-Ethoxyimino-1-methyl-2-[4-(4-trifluoromethyl-benzyloxy)-phenyl]-ethylideneaminooxymethyl}-phenyl)-methoxyimino-acetic acid methyl ester (compound 4.26);
(66) (2-{2-Ethoxyimino-1-methyl-2-[4-(4-trifluoromethyl-benzyloxy)-phenyl]-ethylideneaminooxymethyl}-phenyl)-2-methoxyimino-N-methyl-acetamide (compound 4.27);
(67) {2-Ethoxyimino-1-methyl-2-[4-(2-trifluoromethyl-benzyloxy)-phenyl]-ethylideneaminooxymethyl}-phenyl)-methoxyimino-acetic acid methyl ester (compound 4.28);
(68) (2-{2-Ethoxyimino-1-methyl-2-[4-(2-trifluoromethyl-benzyloxy)-phenyl]-ethylideneaminooxymethyl}-phenyl)-2-methoxyimino-N-methyl-acetamide (compound 4.29);
(69) (2-{2-Ethoxyimino-1-methyl-2-[4-(3-trifluoromethyl-phenoxy)-phenyl]-ethylidene-minooxymethyl}-phenyl)-3-methoxy-acrylic acid methyl ester (compound 4.32);
(70) {2-[4-(4-Chloro-phenoxy)-phenyl]-2-ethoxyimino-1-methyl-ethylideneaminooxymethyl}-phenyl)-methoxyimino-acetic acid methyl ester (compound 4.68);
(71) (2-{2-[4-(4-Chloro-phenoxy)-phenyl]-2-ethoxyimino-1-methyl-ethylideneaminooxymethyl}-phenyl)-2-methoxyimino-N-methyl-acetamide (compound 4.70);
(72) {2-[4-(3,4-Dichloro-phenoxy)-phenyl]-2-ethoxyimino-1-methyl-ethylideneaminooxymethyl}-phenyl)-methoxyimino-acetic acid methyl ester (compound 4.71);
(73) (2-{2-[4-(3,4-Dichloro-phenoxy)-phenyl]-2-ethoxyimino-1-methyl-ethylideneaminooxymethyl}-phenyl)-3-methoxy-acrylic acid methyl ester (compound 4.72);
(74) (2-(2-[4-(3,4-Dichloro-phenoxy)-phenyl]-2-ethoxyimino-1-methyl-ethylideneaminooxymethyl}-phenyl)-2-methoxyimino-N-methyl-acetamide (compound 4.73);
(75) (2-{2-Ethoxyimino-1-methyl-2-[4-(4-trifluoromethyl-phenoxy)-phenyl]-ethylideneaminooxymethyl}-phenyl)-2-methoxyimino-N-methyl-acetamide (compound 4.146);
(76) (2-{2-Ethoxyimino-1-methyl-2-[4-(4-trifluoromethyl-phenoxy)-phenyll-ethylideneaminooxymethyl}-phenyl)-2-methoxyimino-N-methyl-acetamide (compound 4.144);
(77) {2-Ethoxyimino-1-methyl-2-[4-(4-trifluoromethyl-phenoxy)-phenyl]-ethylideneaminooxymethyl}-phenyl)-methoxyimino-acetic acid methyl ester (compound 4.141);
(78) (2-{2-[4-(4-Chloro-benzyloxy)-phenyl]-2-ethoxyimino-1-methyl-ethylideneaminooxymethyl}-phenyl)-3-methoxy-acrylic acid methyl ester (compound 4.66);
(79) (2-{2-[4-(4-Bromo-phenoxy)-phenyl]-2-ethoxyimino-1-methyl-ethylideneaminooxymethyl}-phenyl)-3-methoxy-acrylic acid methyl ester (compound 4.39);
(80) (2-{2-[4-(4-.tert.-Butyl-phenoxy)-phenyl]-2-ethoxyimino-1-methyl-ethylideneaminooxymethyl}-phenyl)-3-methoxy-acrylic acid methyl ester (compound 4.55);
(81) [4-isobutoxy-phenyl]-2-methoxyimino-1-methyl-ethylideneaminooxymethyl}-phenyl)-3-methoxy-acrylic acid methyl ester (compound 1.31);
(82) [4-fluoro-2-methyl-phenyl]-2-methoxyimino-1-methyl-ethylideneaminooxymethyl}-phenyl)-3-methoxy-acrylic acid methyl ester (compound 1.51);
(83) [2-fluoro-4-methyl-phenyl]-2-methoxyimino-1-methyl-ethylideneaminooxymethyl}-phenyl)-3-methoxy-acrylic acid methyl ester (compound 1.57);
(84) [4-cyclopentyloxy-phenyl]-2-methoxyimino-1-methyl-ethylideneaminooxymethyl}-phenyl)-3-methoxy-acrylic acid methyl ester (compound 1.62);
(85) [2-fluoro-4-n-propyloxy-phenyl]-2-methoxyimino-1-methyl-ethylideneaminooxymethyl}-phenyl)-3-methoxy-acrylic acid methyl ester (compound 1.63);
(86) [2-methyl-4-n-propoxy-phenyl]-2-methoxyimino-1-methyl-ethylideneaminooxymethyl}-phenyl)-3-methoxy-acrylic acid methyl ester (compound 1.64);
(87) [2-fluoro-4-ethoxy-phenyl]-2-methoxyimino-1-methyl-ethylideneaminooxymethyl}-phenyl)-3-methoxy-acrylic acid methyl ester (compound 1.70);
(88) [2-fluoro-4-methoxy-phenyl]-2-methoxyimino-1-methyl-ethylideneaminooxymethyl}-phenyl)-3-methoxy-acrylic acid methyl ester (compound 1.72);
(89) [4-ethoxy-2-methyl-phenyl]-2-methoxyimino-1-methyl-ethylideneaminooxymethyl}-phenyl)-3-methoxy-acrylic acid methyl ester (compound 1.79);
(90) 2-Methoxyimino-(2-{2-methoxyimino-1-methyl-2-[4-isobutoxy)-phenyl]-ethylideneaminooxymethyl}-phenyl)-acetic acid methyl ester (compound 2.22);
(91) 2-Methoxyimino-(2-{2-methoxyimino-1-methyl-2-[4-n-propoxy-phenyl]-ethylideneaminooxymethyl}-phenyl)-acetic acid methyl ester (compound 2.23);
(92) 2-Methoxyimino-(2-{2-methoxyimino-1-methyl-2-[4-fluoro-2-methyl-phenyl]-ethylideneaminooxymethyl}-phenyl)-acetic acid methyl ester (compound 2.35);
(93) 2-Methoxyimino-(2-{2-methoxyimino-1-methyl-2-[2-fluoro-4-methyl-phenyl]-ethylideneaminooxymethyl}-phenyl)-acetic acid methyl ester (compound 2.39);
(94) 2-Methoxyimino-(2-{2-methoxyimino-1-methyl-2-[4-cyclopentyloxy-phenyl]-ethylideneaminooxymethyl}-phenyl)-acetic acid methyl ester (compound 2.44);
(95) 2-Methoxyimino-(2-{2-methoxyimino-1-methyl-2-[2-fluoro-4-n-propoxy-phenyl]-ethylideneaminooxymethyl}-phenyl)-acetic acid methyl ester (compound 2.45);
(96) 2-Methoxyimino-(2-{2-methoxyimino-1-methyl-2-[2-methyl-4-n-propoxy-phenyl]-ethylideneaminooxymethyl}-phenyl)-acetic acid methyl ester (compound 2.46);
(97) 2-Methoxyimino-(2-{2-methoxyimino-1-methyl-2-[2-fluoro-4-ethoxy-phenyl]-ethylideneaminooxymethyl}-phenyl)-acetic acid methyl ester (compound 2.49);
(98) 2-Methoxyimino-(2-{2-methoxyimino-1-methyl-2-[2-fluoro-4-methoxy-phenyl]-ethylideneaminooxymethyl}-phenyl)-acetic acid methyl ester (compound 2.52);
(99) 2-Methoxyimino-(2-{2-methoxyimino-1-methyl-2-[4-n-ethoxy-2-methyl-phenyl]-ethylideneaminooxymethyl}-phenyl)-acetic acid methyl ester (compound 2.59);
(100) 2-Methoxyimino-2-(2-{2-methoxyimino-1-methyl-2-[4-isobutoxy-phenyl]-ethylideneaminooxymethy}phenyl)-N-methyl-acetamide (compound 3.22);
(101) 2-Methoxyimino-2-(2-{2-methoxyimino-1-methyl-2-[4-n-propoxy-phenyl]-ethylideneaminooxymethyl}-phenyl)-N-methyl-acetamide (compound 3.23);
(102) 2-Methoxyimino-2-(2-{2-methoxyimino-1-methyl-2-[4-n-butoxy-phenyl]-ethylideneaminooxymethyl}-phenyl)-N-methyl-acetamide (compound 3.24);
(103) 2-Methoxyimino-2-(2-{2-methoxyimino-1-methyl-2-[4-fluoro-2-methyl-phenyl]-ethylideneaminooxymethyl}-phenyl)-N-methyl-acetamide (compound 3.35);
(104) 2-Methoxyimino-2-(2-{2-methoxyimino-1-methyl-2-[2-fluoro-4-methyl-phenyl]-ethylideneaminooxymethyl}-phenyl)-N-methyl-acetamide (compound 3.39);
(105) 2-Methoxyimino-2-(2-{2-methoxyimino-1-methyl-2-[4-cyclopentyloxy-phenyl]-ethylideneaminooxymethyl}-phenyl)-N-methyl-acetamide (compound 3.45);
(106) 2-Methoxyimino-2-(2-{2-methoxyimino-1-methyl-2-[2-fluoro-4-n-propoxy-phenyl]-ethylideneaminooxymethyl}-phenyl)-N-methyl-acetamide (compound 3.46);
(107) 2-Methoxyimino-2-(2-{2-methoxyimino-1-methyl-2-[2-methyl-4-n-propoxy-phenyl]-ethylideneaminooxymethyl}-phenyl)-N-methyl-acetamide (compound 3.47);
(108) 2-Methoxyimino-2-(2-{2-methoxyimino-1-methyl-2-[2-fluoro-4-ethoxy-phenyl]-ethylideneaminooxymethyl}-phenyl)-N-methyl-acetamide (compound 3.50);
(109) 2-Methoxyimino-2-(2-{2-methoxyimino-1-methyl-2-[2-fluoro-4-methoxy-phenyl]-ethylideneaminooxymethyl}-phenyl)-N-methyl-acetamide (compound 3.53); and
(110) 2-Methoxyimino-2-(2-{2-methoxyimino-1-methyl-2-[4-ethoxy-2-methyl-phenyl]-ethylideneaminooxymethyl}-phenyl)-N-methyl-acetamide (compound 3.60).
The compounds of the formula (I) listed in Tables 1 to 158 and, where appropriate, E/Z isomers and E/Z isomer mixtures thereof are particularly preferred in the context of the invention.
The invention furthermore relates to the process for the preparation of the compounds of the formula (I) and, where appropriate, their E/Z isomers, E/Z isomer mixtures and/or tautomers, in each case in the free form or in salt form, for example which comprises
a1) either reacting a compound of the formula: 
which is known or can be prepared by methods known per se and in which
X, Y, Z, R3, R4 and R9 are as defined for formula (I) and
X1 is a leaving group, and in which the provisos mentioned above for the compounds of the formula (I) apply, preferably in the presence of a base, with a compound of the formula: 
in which n, q, A, G, R, R2, R5 and R7 are as defined for formula (I), and in which the provisos mentioned above for the compounds of the formula (I) apply, or
a2) reacting a compound of the formula: 
in which n, q, R, A, G, R2, R5 and R7 are as defined for formula (I), and in which the provisos mentioned above for the compounds of the formula (I) apply, if appropriate in the presence of a base, with a compound of the formula: 
which is known or can be prepared by methods known per se, and in which X, Y, Z, R3, R4 and R9 are as defined for formula (1), or
b) for the preparation of a compound of the formula (I) in which Y is NHR8 and Z is O, reacting a compound of the formula (I) in which Y is OR1 with a compound of the formula R8NH2, which is known or can be prepared by methods known per se and in which R8 is as defined for formula (1), or
c) for the preparation of a compound of the formula (I) in which Y is NHR8 and Z is S, reacting a compound of the formula (I) in which Y is R8NH and Z is O with P4S10 or Lawesson""s reagent, or
d) for the preparation of a compound of the formula (I) in which Z is SO, reacting a compound of the formula (I) in which Z is S with an oxidizing agent, or
e) for the preparation of a compound of the formula (I) in which R5 is aryl-Q-C2-C6alkyl, aryl-Q-C2-C6alkenyl, heterocyclyl-Q-C2-C6alkyl, heterocyclyl-Q-C2-C6alkenyl, or aryl-Q-C2-C6or aryl-Q-C2-C6alkenyl, heterocyclyl-Q-C2-C6alkyl or heterocyclyl-Q-C2-C6alkenyl which are mono- to pentasubstituted in the aryl or heterocyclyl ring, depending on the possibility of substitution, and where the substituents independently of one another are selected from the group consisting of halogen, C1-C6alkyl, halogeno-C1-C6alkyl, C3-C6cycloalkyl, halogeno-C3-C6cycloalkyl, C1-C6alkoxy, halogeno-C1-C6alkoxy, CN, nitro, OC(xe2x95x90O)-C1-C6alkyl, OH, NH2 and C1-C6alkoxycarbonyl;
Q is a direct bond, xe2x80x94CH(OH)xe2x80x94; xe2x80x94C(xe2x95x90O)xe2x80x94 or xe2x80x94S(xe2x95x90O)vxe2x80x94; and
v is 0, 1 or 2,
reacting a compound of the formula: 
in which
X, Y, Z, R3, R4, R9 n, q, R, A, G, R2 and R7 are as defined for formula (I), R5a is aryl-Q-C2-C6alkynyl or heterocyclyl-Q-C2-C6alkynyl, or aryl-Q-C2-C6alkynyl or hetero-cyclyl-Q-C2-C6alkynyl which are mono- to pentasubstituted in the aryl or heterocyclyl ring, depending on the possibility of substitution, and where the substituents independently of one another are chosen from the group consisting of halogen, C1-C6alkyl, halogeno-C1-C6-alkyl, C3-C6cycloalkyl, halogeno-C3-C6-cycloalkyl, C1-C6alkoxy, halogeno-C1-C6-alkoxy, CN, nitro and C1-C6alkoxycarbonyl;
Q is a direct bond, xe2x80x94CH(OH)xe2x80x94, xe2x80x94C(xe2x95x90O)xe2x80x94 or xe2x80x94S(xe2x95x90O)vxe2x80x94; and
v is 0, 1 or 2;
and in which the provisos mentioned above for the compounds of the formula (I) apply; which is known or can be prepared by processes known per se, with hydrogen in the presence of a hydrogenation catalyst,
and in each case, if desired, converting a compound of the formula (I) obtainable according to the process or in another manner or an E/Z isomer or tautomer thereof, in each case in the free form or in salt form, into another compound of the formula (I) or an E/Z isomer or tautomer thereof, in each case in the free form or in salt form, separating a mixture of E/Z isomers obtainable according to the process and isolating the desired isomer, and/or converting a free compound of the formula (I) obtainable according to the process or in another manner or an E/Z isomer or tautomer thereof into a salt or converting a salt, obtainable according to the process or in another manner, of a compound of the formula (I) or of an E/Z isomer or tautomer thereof into the free compound of the formula (I) or an E/Z isomer or tautomer thereof or into another salt.
The invention furthermore relates to the process for the preparation of compounds of the formula (III), in each case in the free form or in salt form, for example which comprises
f) reacting a compound of the formula (IV) in which n, q, A, G, R, R2, R5 and R7 are as defined for formula (I) and in which the provisos mentioned above for the compounds of the formula (I) apply, if appropriate in the presence of a base, with H2NOH or a salt thereof, or
g) reacting a compound of the formula: 
in which n, q, G, R, R2 and R5 are as defined for formula (I)
and in which the provisos mentioned above for the compounds of the formula (I) apply, if appropriate in the presence of a base, with a compound of the formula:
R7ANH2xe2x80x83xe2x80x83(VII),
which is known or can be prepared by methods known per se and in which A and R7 are as defined for formula (I),
and in each case, if desired, converting a compound of the formula (III) obtainable according to the process or in another manner or an E/Z isomer or tautomer thereof, in each case in the free form or in salt form, into another compound of the formula (III) or an E/Z isomer or tautomer thereof, in each case in the free form or in salt form, separating a mixture of E/Z isomers obtainable according to the process and isolating the desired isomers, and/or converting a free compound of the formula (III) obtainable according to the process or in another manner or an E/Z isomer or tautomer thereof into a salt, or converting a salt, obtainable according to the process or in another manner, of a compound of the formula (III) or of an E/Z isomer or tautomer thereof into the free compound of the formula (III) or an E/Z isomer or tautomer thereof or into another salt.
Because of their structure, the compounds of the formulae (III), (IV) and (VI) are particularly suitable for the preparation of the active end products of the formula (I) or other active substances having this part structure. Where they are new, the present invention likewise relates to them.
The statements above for the E/Z isomers and tautomers of compounds of the formulae (I) and (ill) apply in an analogous manner to starting materials defined above and below in respect of E/Z isomers and tautomers thereof.
The reactions described above and below are carried out in a manner known per se, for example in the absence or usually in the presence of a suitable solvent or diluent or of a mixture thereof, the reactions being carried out, as required, with cooling, at room temperature or with heating, for example in a temperature range from about 0xc2x0 C. up to the boiling point of the reaction medium, preferably from about 20xc2x0 C. to about +120xc2x0 C., in particular 60xc2x0 C. to 80xc2x0 C., and, if necessary, in a closed vessel, under pressure, in an inert gas atmosphere and/or under anhydrous conditions. Particularly advantageous reaction conditions can be seen from the examples.
The starting materials defined above and below which are used for the preparation of the compounds of the formula (I) and, where appropriate, their E/Z isomers and tautomers are known or can be prepared by methods known per se, for example according to the instructions below.
Variants a1/a2):
Suitable leaving groups X1 in the compounds of the formula (II) are, for example, hydroxyl, C1-C8alkoxy, halogeno-C1-C8-alkoxy, C1-C8alkanoyloxy, mercapto, C1-C8alkylthio, halogeno-C1-C8-alkylthio, C1-C8alkanesulfonyloxy, halogeno-C1-C8-alkanesulfonyloxy, benzenesulfonyloxy, toluenesulfonyloxy and halogen, preferably toluenesulfonyloxy, trifluoromethanesulfonyloxy and halogen, in particular halogen.
Suitable bases to facilitate the reaction are, for example, alkali metal or alkaline earth metal hydroxides, hydrides, amides, alkanolates, acetates, carbonates, dialkylamides or alkylsilylamides, alkylamines, alkylenediamines, non-alkylated or N-alkylated, saturated or unsaturated cycloalkylamines, basic heterocyclic compounds, ammoniumhydroxides and carboxylic amines. Examples are sodium hydroxide, hydride, amide, methanolate, acetate, and carbonate, potassium tert-butanolate, hydroxide, carbonate and hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)-amide, calcium hydride, triethylamine, diisopropylethyl-amine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide and 1,5-diazabicyclo[5.4.0]undec-5-ene (DBU).
The reaction partners can be reacted with one another as such, i.e. without addition of a solvent or diluent, for example in the melt. Usually, however, the addition of an inert solvent or diluent or of a mixture thereof is advantageous. Examples of such solvents or diluents are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethene or tetrachloroethene; esters, such as ethyl acetate, ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tertbutylmethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethyl ether, tetrahydrofuran or dioxane; ketones, such as acetone, methyl ethyl ketone or methyl isobutyl ketone; alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol or glycerol; amides, such as N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N-methyl-pyrrolidone or hexamethylphosphoric acid triamide; nitriles, such as acetonitrile or propionitrile; and sulfoxides, such as dimethyl sulfoxide. If the reaction is carried out in the presence of a base, bases employed in excess, such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, can also serve as solvents or diluents.
The reaction is advantageously carried out in a temperature range from about 0xc2x0 C. to about 180xc2x0 C., preferably from about 10xc2x0 C. to about 80xc2x0 C., in many cases in the range between room temperature and the reflux temperature of the reaction mixture.
The reaction is preferably carried out under normal pressure.
The reaction can be carried out without an inert gas atmosphere; however, it is preferably carried out under an inert gas atmosphere, for example nitrogen or argon, in particular nitrogen.
The reaction time is not critical; a reaction time of about 0.1 to about 24 hours, in particular about 0.5 to about 2 hours, is preferred.
The product is isolated by customary methods, for example by filtration, crystallization, distillation or chromatography or any suitable combination of these processes.
In a preferred embodiment of variants a1/a2), a compound (II) is reacted with a compound (III) at 0xc2x0 C. to 80xc2x0 C., preferably 10xc2x0 C. to 30xc2x0 C., in an inert solvent, preferably an amide, in particular N,N-dimethylformamide, in the presence of a metal hydride, preferably sodium hydride.
Particularly preferred conditions for the reaction are described in Examples H1d) and H1e).
The compounds of the formula (II) are known or can be prepared analogously to known compounds.
Variant b)
The reaction partners can be reacted with one another as such, i.e. without addition of a solvent or diluent, for example in the melt. Usually, however, the addition of an inert solvent or diluent or of a mixture thereof is advantageous. Examples of such solvents or diluents are those mentioned in variant a1/a2).
The reaction is advantageously carried out in a temperature range from about 0xc2x0 C. to about 180xc2x0 C., preferably from about 10xc2x0 C. to about 80xc2x0 C., in many cases in the range between room temperature and the reflux temperature of the reaction mixture.
The reaction is preferably carried out under normal pressure.
The reaction can be carried out without an inert gas atmosphere; preferably, however, it is carried out under an inert gas atmosphere, for example nitrogen or argon, in particular nitrogen.
The reaction time is not critical; a reaction time of about 0.1 to about 24 hours, in particular about 0.5 to about 2 hours, is preferred,
The product is isolated by customary methods, for example by filtration, crystallization, distillation or chromatography or any suitable combination of these processes.
Variant c)
The reaction partners can be reacted with one another as such, i.e. without addition of a solvent or diluent, for example in the melt. Usually, however, the addition of an inert solvent or diluent or of a mixture thereof is advantageous. Examples of such solvents or diluents are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethene or tetrachloroethene; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethyl ether, tetrahydrofuran or dioxane; and sulfoxides, such as dimethyl sulfoxide.
The reaction is advantageously carried out in a temperature range from about 0xc2x0 C. to about +120xc2x0 C., preferably from about 80xc2x0 C. to about +120xc2x0 C.
The reaction is preferably carried out under normal pressure.
The reaction can be carried out without an inert gas atmosphere; however, it is preferably carried out under an inert gas atmosphere, for example nitrogen or argon, in particular nitrogen.
The reaction time is not critical; a reaction time of about 0.1 to about 24 hours, in particular about 0.5 to about 2 hours, is preferred.
The product is isolated by customary methods, for example by filtration, crystallization, distillation or chromatography or any suitable combination of these processes.
Variant d)
Suitable oxidizing agents are, for example, inorganic peroxides, such as sodium perborate, or hydrogen peroxide, or organic peracids, such as perbenzoic acid or peracetic acid, or mixtures of organic acids and hydrogen peroxide, for example acetic acid/hydrogen peroxide.
The reaction partners can be reacted with one another as such, i.e. without addition of a solvent or diluent, for example in the melt. Usually, however, the addition of an inert solvent or diluent or of a mixture thereof is advantageous. Examples of such solvents or diluents are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethene or tetrachloroethene; esters, such as ethyl acetate; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tertbutyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxy diethyl ether, tetrahydrofuran or dioxane; ketones, such as acetone, methyl ethyl ketone or methyl isobutyl ketone; alcohols, such as methanol, ethanol or propanol; amides, such as N,N-dimethylformamide, N,N-diethyl-formamide, N,N-dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoric acid triamide; nitriles, such as acetonitrile or propionitrile; and sulfoxides, such as dimethyl sulfoxide. If the reaction is carried out in the presence of an organic acid or peracid, acids employed in excess, for example strong organic carboxylic acids, such as C1-C4alkanecarboxylic acids which are unsubstituted or substituted, for example by halogen, for example formic acid, acetic acid or propionic acid, can also serve as the solvent or diluent.
The reaction is advantageously carried out in a temperature range from about 0xc2x0 C. to about +120xc2x0 C., preferably from about 0xc2x0 C. to about +40xc2x0 C.
The reaction is preferably carried out under normal pressure.
The reaction can be carried out without an inert gas atmosphere; however, it is preferably carried out under an inert gas atmosphere, for example nitrogen or argon, in particular nitrogen.
The reaction time is not critical; a reaction time of about 0.1 to about 24 hours, in particular about 0.5 to about 2 hours, is preferred.
The product is isolated by customary methods, for example by filtration, crystallization, distillation or chromatography or any suitable combination of these processes.
Variant e)
Suitable hydrogenation catalysts are, in particular, transition metal catalysts, in particular palladium, ruthenium, rhodium, nickel, zinc or platinum catalysts. Raney nickel, palladium-on-active charcoal and Lindlar catalyst (Pdxe2x80x94CaCO3xe2x80x94PbO) are particularly suitable. However, the hydrogenation can also be carried out in a homogeneous solution, for example in the presence of RhCl(Ph3)3 (Wilkinson""s catalyst).
The reaction partners can be reacted with one another as such, i.e. without addition of a solvent or diluent, for example in the melt. Usually, however, the addition of an inert solvent or diluent or of a mixture thereof is advantageous. Examples of such solvents or diluents are those mentioned in variant a1/a2). Ethers, such as tetrahydrofuran or dioxane, and esters, such as ethyl acetate, are particularly suitable.
The reaction is advantageously carried out in a temperature range from about 0xc2x0 C. to about 80xc2x0 C., preferably from about 1 0xc2x0 C. to about 50xc2x0 C., and in many cases at room temperature.
The reaction is preferably carried out under normal pressure or slightly increased pressure, preferably under normal pressure.
The reaction time is not critical; a reaction time of about 0.1 to about 24 hours, in particular about 0.5 to about 2 hours, is preferred.
The product is isolated by customary methods, for example by filtration, crystallization, distillation or chromatography or any suitable combination of these processes.
Particularly preferred conditions for the reaction are described in Examples H3 a) to c).
Variant f)
Suitable bases for facilitating the reaction are, for example, those mentioned in variant a1/a2).
The reaction partners can be reacted with one another as such, i.e. without addition of a solvent or diluent, for example in the melt. Usually, however, the addition of an inert solvent or diluent or of a mixture thereof is advantageous. Examples of such solvents or diluents are those mentioned in variant a1/a2).
The reaction is advantageously carried out in a temperature range from about 0xc2x0 C. to about 180xc2x0 C., preferably from about 10xc2x0 C. to about 80xc2x0 C., and in many cases in the range between room temperature and the reflux temperature of the reaction mixture.
The reaction is preferably carried out under normal pressure.
The reaction can be carried out without an inert gas atmosphere; however, it is preferably carried out under an inert gas atmosphere, for example nitrogen or argon, in particular nitrogen.
The reaction time is not critical; a reaction time of about 0.1 to about 24 hours, in particular about 0.5 to about 2 hours, is preferred.
The product is isolated by customary methods, for example by filtration, crystallization, distillation or chromatography or any suitable combination of these processes.
Variant g)
Suitable bases for facilitating the reaction are, for example, those mentioned in variant a1/a2).
The reaction partners can be reacted with one another as such, i.e. without addition of a solvent or diluent, for example in the melt. Usually, however, the addition of an inert solvent or diluent or of a mixture thereof is advantageous. Examples of such solvents or diluents are those mentioned in variant a1/a2).
The reaction is advantageously carried out in a temperature range from about 0xc2x0 C. to about 18xc2x0 C., preferably from about 10xc2x0 C. to about 80xc2x0 C., in many cases in the range between room temperature and the reflux temperature of the reaction mixture.
The reaction is preferably carried out under normal pressure.
The reaction can be carried out without an inert gas atmosphere; however, it is preferably carried out under an inert gas atmosphere, for example nitrogen or argon, in particular nitrogen.
The reaction time is not critical; a reaction time of about 0.1 to about 24 hours, in particular about 0.5 to about 2 hours, is preferred.
The product is isolated by customary methods, for example by filtration, crystallization, distillation or chromatography or any suitable combination of these processes.
In a preferred embodiment of variant f), a compound (VI) is reacted with a compound (VII) at 0xc2x0 C. to 120xc2x0 C., preferably 60xc2x0 C. to 120xc2x0 C., in an inert solvent, preferably an amine, in particular pyridine.
The compounds of the formulae (I), (II), (Ill), (IV), (V) and (VI) can be present in the form of one of the possible isomers or as a mixture thereof, for example depending on the number and the absolute and relative configuration of the asymmetric carbon atoms, as pure isomers, such as antipodes and/or diastereomers, or as isomer mixtures, such as enantiomer mixtures, for example racemates, diastereomer mixtures or racemate mixtures; the invention relates both to the pure isomers and to all the possible isomer mixtures and is in each case to be understood accordingly above and below, although stereochemical details are not mentioned specifically in every case.
Because of the physico-chemical differences of the constituents, diastereomer mixtures and racemate mixtures of compounds of the formulae (I), (II), (Ill), (IV), (V) and (VI) obtainable according to the processxe2x80x94depending on the choice of starting substances and proceduresxe2x80x94or in another manner can be separated into the pure diasteromers or racemates in a known manner, for example by fractional crystallization, distillation and/or chromatography.
Correspondingly obtainable enantiomer mixtures, such as racemates, can be separated into the optical antipodes by known methods, for example by recrystallization from an optically active solvent, by chromatography over chiral adsorbents, for example high pressure liquid chromatography (HPLC) on acetylcellulose, with the aid of suitable microorganisms, by cleavage with specific, immobilized enzymes, or via the formation of inclusion compounds, for example using chiral crown ethers, only one enantiomer being complexed.
As well as by separation of corresponding isomer mixtures, pure diastereomers or enantiomers can also be obtained according to the invention by generally known methods of diastereoselective or enantioselective synthesis, for example by carrying out the process according to the invention with educts with correspondingly suitable stereochemistry.
In each case the more biologically active isomer, for example enantiomer, or isomer mixture, for example enanfiomer mixture, is advantageously isolated or synthesized, if the individual components have a different biological activity.
The compounds of the formulae (I), (II), (Ill), (IV), (V) and (VI) can also be obtained in the form of their hydrates and/or include other solvents, for example solvents which may be used for crystallization of compounds present in solid form.
The invention relates to all those embodiments of the process in which a compound obtainable at any stage of the process is used as a starting substance or intermediate product and all or some of the missing steps are carried out, or a starting substance is used in the form of a derivative or salt and/or its racemates or antipodes or, in particular, is formed under the reaction conditions.
In the process of the present invention, those starting substances and intermediates which lead to the compounds of the formula (I) defined above as particularly valuable or preferably used.
The invention particularly relates to the preparation processes described in Examples H1a) to e).
The invention likewise relates to starting substances and intermediate products used according to the invention for the preparation of compounds of the formula (I) and to their use and processes for their preparation, in particular the compounds of the formulae (III), (IV) and (VI), which are novel. In particular, the compounds of the formulae (Ill) and (VI) can be prepared analogously to Examples H1c) and H1b) respectively.
The compounds of the formula (I) according to the invention are already preventively and/or curatively valuable active compounds with a very favourable biocidal spectrum even at low rates of concentration in the field of pest control, and at the same time show favourable tolerance by warm-blooded animals, fish and plants. The active compounds according to the invention are active against all or individual stages of development of normally sensitive and also of resistant animal pests, such as insects and representatives of the order Acarina, and phytopathogenic fungi. The insecticidal, ovicidal and/or acaricidal action of the active compounds according to the invention can manifest itself here directly, i.e. in mortality of the pests, which occurs immediately or only after some time, for example during moulting, or of their eggs, or indirectly, for example in reduced ovi position and/or hatching rate, the good action corresponding to a mortality rate of at least 50 to 60%.
The animal pests mentioned include, for example:
from the order Lepidoptera, for example,
Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyrotaenia spp., Autographa spp., Busseola fusca, Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp., Clysia ambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp., Crocidolomia binotalis, Cryptophlebia leucotreta, Cydia spp., Diatraea spp., Diparopsis castanea, Earias spp., Ephestia spp., Eucosma spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Grapholita spp., Hedya nubiferana, Heliothis spp., Hellula undalis, Hyphantria cunea, Keiferia lycopersicella, Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta, Operophtera spp., Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea, Pectinophora gossypiella, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp., Scirpophaga spp., Sesamia spp., Sparganothis spp., Spodoptera spp., Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni and Yponomeuta spp.;
from the order Coleoptera, for example,
Agriotes spp., Anthonomus spp., Atomaria linearis, Chaetocnema tibialis, Cosmopolites spp., Curculio spp., Dermestes spp., Diabrotica spp., Epilachna spp., Eremnus spp., Leptinotarsa decemlineata, Lissorhoptrus spp., Melolontha spp., Orycaephilus spp., Otiorhynchus spp., Phlyctinus spp., Popillia spp., Psylliodes spp., Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotroga spp., Tenebrio spp., Tribolium spp. and Trogoderma spp.;
from the order Orthoptera, for example,
Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Periplaneta spp. and Schistocerca spp.;
from the order Isoptera, for example,
Reticulitermes spp.;
from the order Psocoptera, for example,
Liposcelis spp.;
from the order Anoplura, for example,
Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.;
from the order Mallophaga, for example,
Damalinea spp. and Trichodectes spp.;
from the order Thysanoptera, for example,
Frankliniella spp., Hercinothrips spp., Taeniothrips spp., Thrips palmi, Thrips tabaci and Scirtothrips aurantii;
from the order Heteroptera, for example,
Cimex spp., Distantiella theobroma, Dysdercus spp., Euchistus spp. Eurygaster spp. Leptocorisa spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella singularis, Scotinophara spp. and Triatoma spp.;
from the order Homoptera, for example,
Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Bemisia tabaci, Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Coccus hesperidum, Empoasca spp., Eriosoma larigerum, Erythroneura spp., Gascardia spp., Laodelphax spp., Lecanium corni, Lepidosaphes spp., Macrosiphus spp., Myzus spp., Nephotettix spp., Nilaparvata spp., Paratoria spp., Pemphigus spp., Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp., Psylla spp., Pulvinaria aethiopica, Quadraspidiotus spp., Rhopalosiphum spp., Saissetia spp., Scaphoideus spp., Schizaphis spp., Sitobion spp., Trialeurodes vaporariorum, Trioza erytreae and Unaspis citri;
from the order Hymenoptera, for example,
Acromyrmex, Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Solenopsis spp. and Vespa spp.;
from the order Diptera, for example,
Aedes spp., Antherigona soccata, Bibio hortulanus, Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Drosophila melanogaster, Fannia spp., Gastrophilus spp., Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Rhagoletis pomonella, Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.;
from the order Siphonaptera, for example,
Ceratophyllus spp. and Xenopsylla cheopis; 
from the order Thysanura, for example,
Lepisma saccharina and
from the order Acarina, for example,
Acarus siro, Aceria sheldoni, Aculus schlechtendali, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Eotetranychus carpini, Eriophyes spp., Hyalomma spp., Ixodes spp., Olygonychus pratensis, Omithodoros spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Tarsonemus spp. and Tetranychus spp.,
The phytopathogenic fungi mentioned include, for example:
from the class of Fungi imperfecti, for example,
Botrytis spp., Pyricularia spp., Helminthosporium spp., Fusarium spp., Septoria spp., Cercospora spp. and Alternaria spp.;
from the class of Basidiomycetes, for example,
Rhizoctonia spp., Hemileia spp. and Puccinia spp.;
from the class of Ascomycetes, for example,
Venturia spp., Erysiphe spp., Podosphaera spp., Monilinia spp. and Uncinula spp.; and
from the class of Oomycetes, for example,
Phytophthora spp., Pythium spp. and Plasmopara spp.,
Using the active compounds according to the invention, in particular, pests of the type mentioned which occur on plants, in particular on useful and ornamental plants in agriculture, in horticulture and in forestry, or on parts, such as fruit, blossom, foliage, stems, tubers or roots, of such plants can be controlled, i.e. checked or destroyed, in some cases parts of plants which grow on later also additionally being protected against these pests.
Target cultures are, in particular, cereals, such as wheat, barley, rye, oats, rice, maize or sorghum; beet, such as sugar-beet or fodder beet; fruit, for example pomaceous fruit, stone fruit and soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; pulses, such as beans, lentils, peas or soya; oil crops, such as oilseed rape, mustard, poppy, olive, sunflower, coconut, castor, cacao or groundnut; cucumber plants, such as pumpkins, cucumbers or melons; fibre plants, such as cotton, flax, hemp or jute; citrus fruits, such as oranges, lemons, grapefruit or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbage varieties, carrots, onions, tomatoes, potatoes or capsicums; laurel plants, such as avocado, cinnamonium or camphor; and tobacco, nuts, coffee, aubergines, sugar-cane, tea, pepper, vines, hops, banana plants, natural rubber plants and ornamental plants.
The active compounds according to the invention are particularly suitable for controlling insects and representatives of the order Acarina, in particular phytopathogenic feeding insects, such as Anthonomus grandis, Diabrotica balteata, Heliothis virescens larvae, Plutella xylostella and Spodoptera littoralis larvae, and spider mites, such as Tetranychus spp., in cotton, fruit, maize, soya, rape and vegetable crops.
Other fields of use of the active compounds according to the invention are the protection of stores and warehouses and of material and in the hygiene sector, in particular the protection of pets and productive livestock against pests of the type mentioned.
The invention therefore also relates to pesticides such as, to be chosen according to the required aims and given circumstances, emulsifiable concentrates, suspension concentrates, directly sprayable or dilutable solutions, spreadable pastes, dilute emulsions, soluble powders, dispersible powders, wettable powders, dusts, granules or encapsulations in polymeric substances which comprisexe2x80x94at leastxe2x80x94one of the active compounds according to the invention.
The active compound is employed in these compositions in the pure form, a solid active compound, for example, in a specific particle size, or, preferably, together withxe2x80x94at leastxe2x80x94one of the auxiliaries customary in formulation technology, such as extenders, for example solvents or solid carriers, or such as surface-active compounds (surfactants). The compositions may also contain UV-stabilizers, such as a benzotriazole-, a benzophenone-, a oxalic acid anilide-, a cinnamic acid- or an s-triazine-derivative.
Solvents are, for example: non-hydrogenated or partly hydrogenated aromatic hydrocarbons, preferably fractions C8 to C12 of alkylbenzenes, such as xylene mixtures, alkylated naphthalenes or tetrahydronaphthalene, aliphatic or cycloaliphatic hydrocarbons, such as paraffins or cyclohexane, alcohols, such as ethanol, propanol or butanol, glycols and ethers and esters thereof, such as propylene glycol, dipropylene glycol ether, ethylene glycol or ethylene glycol monomethyl or -ethyl ether, ketones, such as cyclohexanone, isophorone or diacetone alcohol, strongly polar solvents, such as N-methylpyrrolid-2-one, dimethyl sulfoxide or N,N-dimethylformamide, water, non-epoxidized or epoxidized plant oils, such as non-epoxidized or epoxidized rapeseed, castor, coconut or soya oil, and silicone oils.
The solid carriers used, for example for dusts and dispersible powders, are as a rule natural rock powders, such as calcite, talc, kaolin, montmorillonite or attapulgite. Highly disperse silicic acids or highly disperse absorbent polymers can also be added to improve the physical properties. Granular adsorptive granule carriers are porous types, such as pumice, crushed brick, sepiolite or bentonite, and non-sorbent carrier materials are calcite or sand. A large number of granular materials of inorganic or organic nature can furthermore be used, in particular dolomite or comminuted plant residues.
Surface-active compounds are, depending on the nature of the active compound to be formulated, nonionic, cationic and/or anionic surfactants or surfactant mixtures with good emulsifying, dispersing and wetting properties. The surfactants listed below are to be regarded only as examples; many other surfactants which are customary in formulation technology and are suitable according to the invention are described in the relevant literature.
Nonionic surfactants are, in particular, polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which can contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols. Substances which are furthermore suitable are water-soluble polyethylene oxide adducts, containing 20 to 250 ethylene glycol ether and 10 to 100 propylene glycol ether groups, on propylene glycol, ethylene diaminopolypropylene glycol and alkyl polypropylene glycol having 1 to 10 carbon atoms in the alkyl chain. The compounds mentioned usually contain 1 to 5 ethylene glycol units per propylene glycol unit. Examples are nonylphenol-polyethoxyethanols, castor oil polyglycol ethers, polypropylene-polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Other substances are fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate.
The cationic surfactants are, in particular, quaternary ammonium salts which contain, as substituents, at least one alkyl radical having 8 to 22 C atoms and, as further substituents, lower, non-halogenated or halogenated alkyl, benzyl or lower hydroxyalkyl radicals. The salts are preferably in the form of halides, methyl-sulfates or ethyl-sulfates. Examples are stearyl-trimethyl-ammonium chloride and benzyl-di-(2-chloroethyl)-ethyl-ammonium bromide.
Suitable anionic surfactants can be both water-soluble soaps and water-soluble synthetic surface-active compounds. Suitable soaps are the alkali metal, alkaline earth metal and substituted or unsubstituted ammonium salts of higher fatty acids (C10-C22), such as the sodium or potassium salts of oleic or stearic acid, or of naturally occurring fatty acid mixtures, which can be obtained, for example, from coconut oil or tall oil; and furthermore also the fatty acid methyl-taurine salts. However, synthetic surfactants are more frequently used, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates. The fatty sulfonates and sulfates are as a rule in the form of alkali metal, alkaline earth metal or substituted or unsubstituted ammonium salts and in general have an alkyl radical of 8 to 22 C atoms, alkyl also including the alkyl moiety of acyl radicals; examples are the sodium or calcium salt of ligninsulfonic acid, of dodecylsulfuric acid ester or of a fatty alcohol sulfate mixture prepared from naturally occurring fatty acids. These also include the salts of sulfuric acid esters and sulfonic acids of fatty alcoholethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and a fatty acid radical having about 8 to 22 C atoms. Alkylarylsulfonates are, for example, the sodium, calcium or triethanolammonium salts of dodecylbenzenesulfonic acid, of dibutyinaphthalenesulfonic acid or of a naphthalenesulfonic acidformaldehyde condensation product. Corresponding phosphates, such as salts of the phosphoric acid ester of a p-nonylphenol-(4-14)-ethylene oxide adduct or phospholipids, can further also be used.
The compositions as a rule comprise 0.1 to 99%, in particular 0.1 to 95%, of active compound and 1 to 99.9%, in particular 5 to 99.9%, ofxe2x80x94at leastxe2x80x94one solid or liquid auxiliary, it being possible as a rule for 0 to 25%, in particular 0.1 to 20%, of the composition to be surfactants (% is in each case per cent by weight). While concentrated compositions are more preferred as commercial goods, the end user as a rule uses dilute compositions which comprise considerably lower concentrations of active compound. Preferred compositions are composed, in particular, as follows (%=per cent by weight):
Emulsifiable concentrates:
Active compound: 1 to 90%, preferably 5 to 20%
Surfactant: 1 to 30%, preferably 10 to 20%
Solvent: 5 to 98%, preferably 70 to 85%
Dusts:
Active compound: 0.1 to 10%, preferably 0.1 to 1%
Solid carrier 99.9 to 90%, preferably 99.9 to 99%
Suspension concentrates:
Active compound: 5 to 75%, preferably 10 to 50%
Water: 94 to 24%, preferably 88 to 30%
Surfactant: 1 to 40%, preferably 2 to 30%
Wettable powders:
Active compound: 0.5 to 90%, preferably 1 to 80%
Surfactant: 0.5 to 20%, preferably 1 to 15%
Solid carrier 5 to 99%, preferably 15 to 98%
Granules:
Active compound: 0.5 to 30%, preferably 3 to 15%
Solid carrier 99.5 to 70%, preferably 97 to 85%
The action of the compositions according to the invention can be extended considerably and adapted to given circumstances by addition of other insecticidal, acaricidal and/or fungicidal active compounds. Active compound additions here are, for example, representatives of the following classes of active compounds: organic phosphorus compounds, nitrophenols and derivatives, formamidines, ureas, carbamates, pyrethroids, chlorinated hydrocarbons and Bacillus thuringiensis preparations. The compositions according to the invention can also comprise further solid or liquid auxiliaries, such as stabilizers, for example non-epoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), defoamers, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, as well as fertilizers or other active compounds for achieving special effects, for example bactericides, nematicides, molluscicides or selective herbicides.
The compositions according to the invention are prepared in a known manner, in the absence of auxiliaries, for example, by grinding and/or sieving a solid active compound or active compound mixture, for example to a particular particle size, and if at least one auxiliary is present, for example, by intimate mixing and/or grinding of the active compound or active compound mixture with the auxiliary or auxiliaries. The invention likewise relates to these processes for the preparation of the compositions according to the invention and the use of the compounds of the formula (I) for the preparation of these compositions.
The invention furthermore relates to the methods of application for the compositions, i.e. the methods for controlling pests of the type mentioned, such as, to be chosen according to the intended aims and given circumstances, spraying, atomizing, dusting, brushing, dressing, scattering or pouring, and to the use of the compositions for controlling pests of the type mentioned. Typical rates of concentration here are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active compound. The rates of application per hectare are in general 1 to 2000 g of active compound per hectare, in particular 10 to 1000 g/ha, preferably 20 to 600 g/ha.
A preferred method of application in the field of crop protection is application to the foliage of the plants (foliar application), where the application frequency and rate of application can be determined according to the danger of infestation by the particular pests. However, the active compound can also enter the plants via the root system (systemic action) by soaking the locus of the plants with a liquid composition or incorporating the active compound in solid form into the locus of the plants, for example into the soil, for example in the form of granules (soil application). In paddy rice crops, such granules can be metered into the flooded rice field.
The compositions according to the invention are also suitable for protection of plant propagation material, for example seed, such as fruit, tubers or grain, or plant seedlings, against fungal infections and animal pests. In this case, the propagation material can be treated with the composition before planting out, and seed, for example, can be dressed before sowing. The active compounds according to the invention can also be applied to seed grains (coating) either by soaking the grains in a liquid composition or coating them with a solid composition. The composition can also be applied to the site of planting out during planting out of the propagation material, for example into the seed furrow during sowing. The invention furthermore relates to these treatment methods for plant propagation material and the plant propagation material thus treated.
The following examples serve to illustrate the invention. They do not limit the invention. Temperatures are stated in degrees Celsius.